Supporting Information

Supporting Information Asymmetric Synthesis of α-aminoboronic Acid Derivatives by Copper-Catalyzed Enantioselective Hydroamination Daiki ishikawa, Koji Hirano,* and Masahiro Miura* Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan k_hirano@chem.eng.osaka-u.ac.jp; miura@chem.eng.osaka-u.ac.jp Contents Instrumentation and Chemicals S1 2 Experimental Procedures S3 S7 Detailed Optimization Studies S8 S10 Stereochemical Assignment S11 Chiral HPLC Charts S12 S36 Characterization Data for Products S37 S121 References S122 Instrumentation and Chemicals 1 H, 13 C, 11 B, and 19 F MR spectra were recorded at 400 MHz, 100 MHz, 128 MHz, and 376 MHz, respectively, for C 6 D 6 or CDCl 3 solutions. HRMS data were obtained by APCI. TLC analyses were performed on commercial glass plates bearing 0.25-mm layer of Wako H 2 Silica Gel 60F 254. H 2 silica gel (Wakogel, 50H 2 ) was used for column chromatography. Unless otherwise noted, materials obtained from commercial suppliers were used without further purification. Anhydrous Cu(OAc) 2 was purchased from Wako Pure Chemical Co. (R)-DTBM-SEGPHOS was obtained from TCI. LiO-t-Bu and PMHS were available from Aldrich. The alkenyl dan boronates 1 were prepared from the corresponding terminal alkynes according to the literature (see the following experimental procedure). S1 O-Benzoyl-,-diethylhydroxylamine (2i) was obtained by the reaction of,-diethylhydroxylamine with benzoyl chloride, while other O-benzoyl-,-dialkylhydroxylamines 2 were synthesized through the nucleophilic substitution of the corresponding amines with benzoyl peroxide. S2 All reactions were carried out under nitrogen S1

atmosphere unless otherwise noted. S2

Experimental Procedures 1. Preparation of Alkenyl dan Boronates 1 Procedure A C 6 H 13 + H BBr 2 SMe 2 CH 2 Cl 2 0 C to rt, 4 h sat. aqueous H 4 Cl 0 C to rt, 1 h 86% C 6 H 13 B(OH) 2 H 2 H 2 H B(dan) C MS 4A, toluene B 6 H 13 C reflux, 2 h 6 H 13 H 1a 88% 76% in two steps Synthesis of 1a is representative: To a solution of 1-octyne (1.47 ml, 10 mmol) in CH 2 Cl 2 (5 ml) was added HBBr 2 SMe 2 (1 M in CH 2 Cl 2, 10 ml, 10 mmol) at 0 C. The mixture was then brought to room temperature and stirred for 4 h. The resulting mixture was quenched with saturated aq. H 4 Cl at 0 C. After warming to room temperature, the suspension was stirred for additional 1 h. The resulting mixture was extracted with Et 2 O, and the organic layer was washed with aq. ahco 3. After additional extraction with Et 2 O, the combined organic layers were dried over sodium sulfate. Filtration of sodium sulfate and concentration in vacuo gave (E)-oct-1-en-1-ylboronic acid (1.3 g, 8.6 mmol) in 86% yield. The crude material was used for the next step without further purification. (E)-Oct-1-en-1-ylboronic acid (1.3 g, 8.6 mmol), 1,8-diaminonaphthalene (1.4 g, 8.6 mmol), molecular sieve 4A (ca. 8.0 g), and toluene (60 ml) were placed in a 200 ml recovery flask equipped with a reflux condenser, and the mixture was stirred at 110 C for 2 h under air. After cooling to room temperature, the resulting mixture was filtered through a pad of Celite. The filtrate was quenched with water and extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate. After filtration of sodium sulfate and concentration in vacuo, silica gel column purification (Silica gel 60, spherical neutral, obtained from Kanto Chemical) with hexane/ethyl acetate (40/1, v/v) afforded (E)-2-(oct-1-en-1-yl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (1a, 2.1 g, 7.6 mmol) in 88% yield. The overall yield is 76%. The alkenyl dan boronates 1b f were prepared by the same procedure. S3

Procedure B B(OH) 2 + H 2 H 2 FeCl 3, imidazole MeC/H 2 O, rt, 6 h H B H B(dan) 1g 88% Synthesis of 1g is representative: To a solution of (E)-styrylboronic acid (0.74 g, 5.0 mmol, commercially available from Aldrich) in MeC (20 ml) was added a solution of FeCl 3 (81 mg, 0.50 mmol) in H 2 O (5 ml) at room temperature. Subsequently, imidazole (1.0 g, 15 mmol) and 1,8-diaminonaphthalene (1.6 g, 10 mmol) were added in one portion. The solution was stirred for 6 h at the same temperature under nitrogen. The resulting mixture was filtered through a pad of Celite, and the filter cake was washed with ethyl acetate. The filtrate was diluted with H 2 O and extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate. After filtration of sodium sulfate and concentration in vacuo, silica gel column purification (Silica gel 60, spherical neutral, obtained from Kanto Chemical) with hexane/dichloromethane/triethylamine (5/1/0.5, v/v/v) afforded (E)-2-styryl-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (1g, 1.2 g, 4.4 mmol) in 88% yield. The alkenyl dan boronates 1h and 1i were prepared by the same procedure. The corresponding staring boronic acids were purchased from Aldrich. Procedure C MeO + TMS I PdCl 2 (PPh 3 ) 2 /CuI Et 3, rt, 4 h quant. MeO TMS K 2 CO 3 MeOH, rt, 2 h quant. MeO H O B O THF, reflux, 16 h 50% H 2 H 2 FeCl 3, imidazole MeC/H 2 O, rt, 6 h MeO 60% H B H MeO 1j B(dan) 30% in four steps Synthesis of 1j: 1-Iode-4-methoxybenzene (2.3 g, 10 mmol), PdCl 2 (PPh 3 ) 2 (0.14 g, 0.20 mmol), and CuI (57mg, 0.60mmol) were placed in a 50 ml two-necked reaction flask, which was filled S4

with nitrogen by using the standard Schlenk technique. Et 3 (30 ml) was then added to the flask, and the suspension was stirred at ambient temperature for 5 min, at which time trimethylsilylacetylene (1.7 ml, 12 mmol) was added and the stirring was continued for another 4 h. The reaction mixture was filtered through a pad of Celite, and the filtrate was quenched with 1 M aqueous HCl. The resulting mixture was extracted with ethyl acetate, and the combined organic layers were dried over sodium sulfate. Filtration of sodium sulfate, concentration in vacuo, and silica gel column purification (Wakosil C-200, obtained from Wako Pure Chemical Co.) with hexane/ethyl acetate (20/1, v/v) gave ((4-methoxyphenyl)ethynyl)trimethylsilane quantitatively. To ((4-methoxyphenyl)ethynyl)trimethylsilane obtained above in 100 ml recovery flask were added potasium carbonate (2.1 g, 15 mmol) and methanol (20 ml), and the suspension was stirred at ambient temperature for 2 h under air. The mixture was quenched with water and extracted with ethyl acetate, and the combined organic layers were dried over sodium sulfate. Filtration of sodium sulfate, concentration in vacuo, and silica gel column purification (Wakosil C-200, obtained from Wako Pure Chemical Co.) with hexane/ethyl acetate (20/1, v/v) afforded 1-ethynyl-4-methoxybenzene quantitatively. A two-necked flask equipped with a reflux condenser was flushed with nitrogen, in which a solution of 1-ethynyl-4-methoxybenzene (1.3 g, 10 mmol) in THF (40 ml) was placed. Catecholborane (1 M in THF, 15 ml, 15 mmol) was then added dropwise, and the mixture was stirred at 70 C for 16 h. The resulting solution was quenched with saturated aq. H 4 Cl. The mixture was extracted with ethyl acetate, and the combined organic layers were dried over sodium sulfate. Filtration of sodium sulfate followed by concentration in vacuo gave (E)-2-(4-methoxystyryl)benzo[d][1,3,2]dioxaborole (1.3 g, 5.0 mmol) in 50% yield. The crude material was used for the next step without further purification. To a solution of (E)-2-(4-methoxystyryl)benzo[d][1,3,2]dioxaborole (1.3 g, 5.0 mmol) in MeC (20 ml) were added a solution of FeCl 3 (81 mg, 0.50 mmol) in H 2 O (5 ml), imidazole (1.0 g, 15 mmol), and 1,8-diaminonaphthalene (1.6 g, 10 mmol) sequentially. The resulting mixture was stirred at room temperature for 6 h before being quenched with water. The mixture was extracted with ethyl acetate, and the combined organic layers were dried over sodium sulfate. Filtration of sodium sulfate, concentration in vacuo, and silica gel column purification (Silica gel 60, spherical neutral, obtained from Kanto Chemical) with hexane/dichloromethane/triethylamine (2/1/0.03, v/v/v) afforded (E)-2-(4-methoxystyryl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (1j, 0.90 g, 3.0 mmol) in 60% yield. The overall yield is 30%. S5

2. Cu-Catalyzed onenantioselective Hydroamination of Alkenyl dan Boronates Synthesis of 3aa (Scheme 2): Cu(OAc) 2 (4.5 mg, 0.025 mmol), 1,2-bis[bis{3,5-di(trifluromethyl)phynyl}phosphino]benzene (CF 3 -dppbz, 25 mg, 0.025 mmol), and LiO-t-Bu (80 mg, 1.0 mmol) were placed in a 20 ml two-necked reaction flask, which was filled with nitrogen by using the Schlenk technique. 1,2-Dichloroethane (0.50 ml) was then added to the flask, and the suspension was stirred for 15 min at ambient temperature. Polymethylhydrosiloxane (PMHS, 50 µl, 0.75 mmol based on Si-H) and a solution of (E)-2-(oct-1-en-1-yl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (1a, 84 mg, 0.30 mmol) and morpholino benzoate (2a, 52 mg, 0.25 mmol) in 1,2-dichroloethane (1.0 ml) were sequentially added dropwise. The solution was stirred at ambient temperature for additional 4 h. The resulting mixture was filtered through a short pad of sodium sulfate and neutral alumina. After evaporation of the volatile materials, the residue was purified by column chromatography on H 2 silica gel with hexane/ethyl acetate (5/1, v/v) to yield 4-(1-(1H-naphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)octyl)morpholine (3aa, 91 mg, 0.25 mmol) quantitatively. 3. Cu-Catalyzed Enantioselective Hydroamination of Alkenyl dan Boronates Synthesis of 3aa (Table 1, entry 1) is representative: Cu(OAc) 2 (4.5 mg, 0.025 mmol), (R)-DTBM-SEGPHOS (30 mg, 0.025 mmol), and LiO-t-Bu (80 mg, 1.0 mmol) were placed in a 20 ml two-necked reaction flask, which was filled with nitrogen by using the Schlenk technique. THF (0.50 ml) was then added to the flask, and the suspension was stirred for 15 min at ambient temperature. Polymethylhydrosiloxane (PMHS, 50 µl, 0.75 mmol based on Si-H) and a solution of (E)-2-(oct-1-en-1-yl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (1a, 84 mg, 0.30 mmol), and morpholino benzoate (2a, 52 mg, 0.25 mmol) in THF (1.0 ml) were sequentially added dropwise. The solution was stirred at ambient temperature for additional 4 h. The resulting mixture was filtered through a short pad of sodium sulfate and neutral alumina. After evaporation of the volatile materials, the residue was purified by column chromatography on H 2 silica gel with hexane/ethyl acetate (5/1, v/v) to yield (R)-4-(1-(1H-naphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)octyl)morpholine (3aa, 61 mg, 0.17 mmol) in 67% yield. The enantiomeric ratio was determined to be 96:4 by chiral HPLC analysis on a chiral stationary phase. 4. Conversion of B(dan) to Bpin (Scheme 5) To a solution of S6

,-dibenzyl-2-(4-methoxyphenyl)-1-(1h-naphtho[1,8-de][1,3,2]diazaborinin-2(3h)-yl)ethan-1-amine (3jk, 93 mg, 0.19 mmol, 99:1 er) and pinacol (89 mg, 0.75 mmol) in THF (1.0 ml) was added 5 M aqueous HCl (0.15 ml, 0.75 mmol), and the resulting mixture was stirred for 12 h. The resulting mixture was filtered through a pad of Celite, and the filter cake was washed with Et 2 O. The filtrate was neutralized with saturated aq. ahco 3, and then extracted with Et 2 O three times. The combined organic layer was dried over sodium sulfate, filtered off, and concentrated in vacuo. The residual pinacol was removed under high vacuum at 80 C for 8 h to form,-dibenzyl-2-(4-methoxyphenyl)-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethan-1-amine (3jk-Bpin, 53 mg, 0.12 mmol) in 62% yield. The enantiomeric ratio was preliminary assigned to be >88:12 by chiral HPLC analysis on a chiral stationary phase. The correct er value could not be determined because of relative instability of 3jk-Bpin under HPLC analytical conditions. S7

Detailed Optimization Studies Table S1. Optimization Studies for Cu-Catalyzed onenantioselective Hydroamination of Alkenyl Boronates 1 with PMHS and Morpholino Benzoate (2a) [a] C 6 H 13 1 B + PMHS + BzO O (3.0 equiv) 2a (1.5 equiv) 10 mol % Cu(OAc) 2 10 mol % ligand LiO-t-Bu (4.0 equiv) DCE, rt, 4 h C 6 H 13 entry B (1) ligand 3, yield (%) [b] 1 B(dan) (1a) CF 3 -dppbz 3aa, (85) 2 B(dan) (1a) dppbz 3aa, 8 3 B(dan) (1a) F 3 -dppbz 3aa, 0 4 B(dan) (1a) MeO-dppbz 3aa, 19 5 B(dan) (1a) DTBM-dppbz 3aa, 0 6 B(dan) (1a) dppe 3aa, 12 7 B(dan) (1a) P[3,5-(CF 3 ) 2 C 6 H 3 ] 3 3aa, 0 8 [c] B(dan) (1a) CF 3 -dppbz 3aa, (>99) 9 [d] B(dan) (1a) CF 3 -dppbz 3aa, 0 10 [c] B(pin) (1a-Bpin) CF 3 -dppbz 3aa-Bpin, 0 11 [c] B(MIDA) (1a-B(MIDA)) CF 3 -dppbz 3aa-B(MIDA), 0 [a] Reaction conditions: Cu(OAc) 2 (0.025 mmol), ligand (0.025 mmol for bisphosphines, 0.050 mmol for monophosphines), 1 (0.25 mmol), 2a (0.38 mmol), PMHS (0.75 mmol based on SiH), LiO-t-Bu (1.0 mmol), DCE (1.5 ml), 2, rt, 4 h. [b] Yield estimated by 1 H MR. Yield of isolated product given in parenthesis. [c] With 1 (0.30 mmol) and 2a (0.25 mmol). [d] Without LiO-t-Bu. O B 3 B(dan) = H B H B(pin) = O B O B(MIDA) = Me B O O O O Me Si O H PMHS n PAr 2 PAr 2 Ar = 3,5-(CF 3 ) 2 C 6 H 3 : CF 3 -dppbz Ar = Ph: dppbz Ar = 3,4,5-F 3 C 6 H 2 : F 3 -dppbz Ph 2 P PPh 2 Ar = 4-MeOC 6 H 4 : MeO-dppbz dppe Ar = 3,5-(t-Bu) 2-4-MeOC 6 H 2 : DTBM-dppbz S8

Table S2. Optimization Studies for Cu-Catalyzed Enantioselective Hydroamination of Alkenyl dan Boronate 1a with PMHS and Morpholino Benzoate (2a) [a] C 6 H 13 B(dan) 1a (1.2 equiv) + PMHS + BzO O (3.0 equiv) 2a 10 mol % Cu 10 mol % ligand LiO-t-Bu (4.0 equiv) solvent, rt, 4 h C 6 H 13 * O B(dan) 3aa entry Cu/ligand solvent yield (%), er [b] 1 CuCl/(S,S)-Me-DuPhos THF 51, 46:54 2 CuCl/(S,S)-Et-DuPhos THF 13, 49:51 3 CuCl/(R,R)-i-Pr-DuPhos THF 30, 44:56 4 CuCl/(R,R)-Ph-BPE THF 44, 47:53 5 CuCl/(S,S,R,R)-Tangphos THF 29, 55:45 6 CuCl/(R,R)-QuinoxP* THF 17, 50:50 7 CuCl/(S,S)-Chiraphos THF 33, 49:51 8 CuCl/(R,Sp)-Joshiphos THF 27, 57:43 9 CuCl/(R)-BIAP THF 53, 82:18 10 CuCl/(R)-Xyl-BIAP THF 62, 71:29 11 CuCl/(R)-MeO-BIPHEP THF 34, 90:10 12 CuCl/(R)-DTBM-MeO-BIPHEP THF 31, 95:5 13 CuCl/(R)-SEGPHOS THF 32, 88:12 14 CuCl/(R)-DTBM-SEGPHOS THF 12, 91:9 15 CuCl/(R)-DTBM-MeO-BIPHEP CPME 15, 95:5 16 CuCl/(R)-DTBM-SEGPHOS CPME 69, 96:4 17 CuCl/(R)-DTBM-SEGPHOS 1,4-dioxane 8, 93:7 18 CuCl/(R)-DTBM-SEGPHOS DME 32, 94:6 19 CuCl/(R)-DTBM-SEGPHOS Et 2 O 52, 96:4 20 CuCl/(R)-DTBM-SEGPHOS t-buome 64, 95:5 21 CuCl/(R)-DTBM-SEGPHOS DCE 24, 94:6 S9

22 CuCl/(R)-DTBM-SEGPHOS toluene 35, 96:4 23 Cu(OAc) 2 /(R)- DTBM-MeO-BIPHEP THF 49, 93:7 24 Cu(OAc) 2 /(R)-DTBM-SEGPHOS THF 67, 96:4 25 Cu(OAc) 2 /(R)-DTBM-SEGPHOS CPME 63, 96:4 26 [c] CuCl/(R)-DTBM-SEGPHOS CPME 0, 27 [c] Cu(OAc) 2 /(R)-DTBM-SEGPHOS THF 0, [a] Reaction conditions: Cu (0.025 mmol), ligand (0.025 mmol), 1a (0.30 mmol), 2a (0.25 mmol), PMHS (0.75 mmol based on SiH), LiO-t-Bu (1.0 mmol), solvent (1.5 ml), 2, rt, 4 h. [b] Yield of isolated product given in parenthesis. The enantiomeric ratio was determined by HPLC analysis on a chiral stationary phase. [c] Without LiO-t-Bu. R R P P R R H P H P tbu tbu (S,S,R,R)-Tangphos R = Me: (S,S)-Me-DuPhos R = Et: (S,S)-Et-DuPhos R = i-pr: (R,R)-i-Pr-DuPhos tbu P Me P tbu Me (R,R)-QuinoxP* Ph 2 P PPh 2 (S,S)-Chiraphos Ph Ph P P Ph Ph (R,R)-Ph-BPE PCy Ph 2 P 2 Fe (R,Sp)-Joshiphos O PAr 2 PAr 2 MeO MeO PAr 2 PAr 2 O O PAr 2 PAr 2 Ar = Ph: (R)-BIAP Ar = 3,5-Me 2 C 6 H 3 : (R)-Xyl-BIAP Ar = Ph: (R)-MeO-BIPHEP Ar = 3,5-(t-Bu) 2-4-MeO-C 6 H 2 : (R)-DTBM-MeO-BIPHEP O Ar = Ph: (R)-SEGPHOS Ar = 3,5-(t-Bu) 2-4-MeO-C 6 H 2 : (R)-DTBM-SEGPHOS As shown in Table S1, we identified two optimized conditions (entries 16 and 24). However, the CuCl/(R)-DTBM-SEGPHOS/CPME system (entry 16) was immediately found to be too specific for the reaction of 1a with 2a. Thus, as seen in the main manuscript, we performed the enantioselective hydroamination with more general Cu(OAc) 2 /(R)-DTBM-SEGPHOS/THF system (entry 24). S10

Stereochemical Assignment The absolute configuration of 3jh was determined to be R by X-ray analysis (Figure S1). X-ray quality crystals were grown from heptane/ethyl acetate. Crystallographic data for the structure has been deposited to the Cambridge Crystallographic Data Center (CCDC 1425245). The specific rotation of a 90:10 enantiomeric mixture of 3jh was [α] 20 D +43 (c 1.0, EtOAc). The absolute configurations of other products were tentatively assigned by analogy. B(dan) MeO S (R)-3jh (90:10 er) [!] 20 D +43 (c 1.0, EtOAc) Figure S1. ORTEP drawing and specific rotation of (R)-3jh. S11

Chiral HPLC Charts 3aa: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 90/10 n-hexane/2-propanol, 0.5 ml/min, major isomer: t R = 17.5 min, minor isomer: t R = 23.8 min, UV detection at 350 nm, 30 o C). rac-3aa Peak # Ret. Time Area Area % 1 17.652 54037057 49.69 2 23.428 54715691 50.31 (R)-3aa Peak # Ret. Time Area Area % 1 17.500 107874780 95.76 2 23.839 4772159 4.24 S12

3ba: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 88/12 n-hexane/2-propanol, 0.5 ml/min, major isomer: t R = 40.8 min, minor isomer: t R = 37.7 min, UV detection at 350 nm, 30 o C). rac-3ba Peak # Ret. Time Area Area % 1 37.616 18619382 49.90 2 41.599 18691453 50.10 (R)-3ba Peak # Ret. Time Area Area % 1 37.713 1204437 1.96 2 40.774 60148905 98.04 S13

3ca: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 85/15 n-hexane/2-propanol, 0.5 ml/min, major isomer: t R = 14.6 min, minor isomer: t R = 25.3 min, UV detection at 350 nm, 30 o C). rac-3ca Peak # Ret. Time Area Area % 1 14.721 19362684 49.81 2 25.186 19511585 50.19 (R)-3ca Peak # Ret. Time Area Area % 1 14.632 54257179 92.31 2 25.345 4517202 7.69 S14

3da: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 85/15 n-hexane/2-propanol, 0.5 ml/min, major isomer: t R = 14.8 min, minor isomer: t R = 23.0 min, UV detection at 350 nm, 30 o C). rac-3da Peak # Ret. Time Area Area % 1 15.106 56481199 50.20 2 22.556 56020771 49.80 (R)-3da Peak # Ret. Time Area Area % 1 14.813 135969498 94.60 2 22.960 7757229 5.40 S15

3ea: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 85/15 n-hexane/2-propanol, 0.5 ml/min, major isomer: t R = 14.9 min, minor isomer: t R = 21.1 min, UV detection at 350 nm, 30 o C). rac-3ea Peak # Ret. Time Area Area % 1 15.083 6066305 50.03 2 21.118 6059152 49.97 (R)-3ea Peak # Ret. Time Area Area % 1 14.912 51503288 88.70 2 21.065 6563704 11.30 S16

3fa: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 88/12 n-hexane/2-propanol, 0.5 ml/min, major isomer: t R = 27.2 min, minor isomer: t R = 35.6 min, UV detection at 350 nm, 30 o C). rac-3fa Peak # Ret. Time Area Area % 1 27.133 64811315 49.95 2 34.521 64947100 50.05 (R)-3fa Peak # Ret. Time Area Area % 1 27.150 39339990 96.62 2 35.563 1375228 3.38 S17

3ga: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 85/15 n-hexane/2-propanol, 0.5 ml/min, major isomer: t R = 28.0 min, minor isomer: t R = 31.8 min, UV detection at 350 nm, 30 o C). rac-3ga Peak # Ret. Time Area Area % 1 27.763 26109174 49.95 2 31.289 26158838 50.05 (R)-3ga Peak # Ret. Time Area Area % 1 27.957 8045388 94.42 2 31.768 475852 5.58 S18

3ha: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 85/15 n-hexane/2-propanol, 0.5 ml/min, major isomer: t R = 31.7 min, minor isomer: t R = 35.3 min, UV detection at 350 nm, 30 o C). rac-3ha Peak # Ret. Time Area Area % 1 31.547 26795172 49.76 2 34.441 27055625 50.24 (R)-3ha Peak # Ret. Time Area Area % 1 31.726 13121956 98.55 2 35.293 192494 1.45 S19

3ia: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 85/15 n-hexane/2-propanol, 0.5 ml/min, major isomer: t R = 46.5 min, minor isomer: t R = 41.7 min, UV detection at 330 nm, 30 o C). rac-3ia 1A161 1A1D1 01A832 0DA203 1A121 1A101 9G 1A1/1 1A131 1A141 1A111 1A11 2A11 41A11 42A11 31A11 32A11 /1A11 /2A11 01A11 02A11 21A11 22A11 D1A11 Peak # Ret. Time Area Area % 1 40.825 4534806 50.10 2 46.542 4516986 49.90 (R)-3ia 1@31 0E@022 1@42 8H 1@41 1@12 1@11 04@634 1@11 2@11 41@11 42@11 31@11 32@11 /1@11 /2@11 01@11 02@11 21@11 22@11 E1@11 Peak # Ret. Time Area Area % 1 41.721 86344 0.45 2 46.455 19168399 99.55 S20

3ia : The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 88/12 n-hexane/2-propanol, 0.5 ml/min, major isomer: t R = 39.1 min, minor isomer: t R = 41.6 min, UV detection at 300 nm, 30 o C). rac-3ia 1A102 1A101 1A1/2 />A3D3 04AD36 1A1/1 1A132 8H 1A131 1A142 1A141 1A112 1A111 1A11 2A11 41A11 42A11 31A11 32A11 /1A11 /2A11 01A11 02A11 21A11 22A11 Peak # Ret. Time Area Area % 1 39.282 2919578 49.84 2 41.827 2938533 50.16 Chiral-3ia 1@121 /C@4/2 1@101 1@1/1 8H 1@131 1@141 1@111 04@E1/ 1@11 2@11 41@11 42@11 31@11 32@11 /1@11 /2@11 01@11 02@11 21@11 22@11 E1@11 Peak # Ret. Time Area Area % 1 39.135 3571468 95.86 2 41.603 154121 4.14 S21

3ab: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALPAK AD-H column, 97/3 n-hexane/2-propanol, 0.5 ml/min, major isomer: t R = 10.2 min, minor isomer: t R = 13.9 min, UV detection at 270 nm, 30 o C). rac-3ab Peak # Ret. Time Area Area % 1 10.580 23689775 48.93 2 14.249 24722977 51.07 (R)-3ab Peak # Ret. Time Area Area % 1 10.248 17010478 96.63 2 13.902 593321 3.37 S22

3ac: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 95.5/0.5 n-hexane/2-propanol, 0.5 ml/min, major isomer: t R = 24.6 min, minor isomer: t R = 11.1 min, UV detection at 300 nm, 30 o C). rac-3ac Peak # Ret. Time Area Area % 1 11.166 56632380 49.40 2 25.575 58014100 50.60 (R)-3ac Peak # Ret. Time Area Area % 1 11.090 12363666 5.66 2 24.617 206135098 94.34 S23

3jd: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 85/15 n-hexane/2-propanol, 0.5 ml/min, major isomer: t R = 13.4 min, minor isomer: t R = 12.1 min, UV detection at 270 nm, 30 o C). rac-3jd Peak # Ret. Time Area Area % 1 11.296 44659675 50.10 2 13.398 44488485 49.90 (R)-3jd Peak # Ret. Time Area Area % 1 12.112 327229 0.50 2 13.357 64611040 99.50 S24

3ae: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 90/10 n-hexane/2-propanol, 0.5 ml/min, major isomer: t R = 15.0 min, minor isomer: t R = 17.4 min, UV detection at 270 nm, 30 o C). rac-3ae Peak # Ret. Time Area Area % 1 14.896 21336205 49.68 2 17.000 21611537 50.32 (R)-3ae Peak # Ret. Time Area Area % 1 14.966 15607868 96.89 2 17.436 500810 3.11 S25

3cf: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 92/8 n-hexane/2-propanol, 1 ml/min, major isomer: t R = 10.9 min, minor isomer: t R = 12.9 min, UV detection at 350 nm, 30 o C). rac-3cf 1A132 1A131 44A166 43AD/4 1A142 :G 1A141 1A112 1A111 1A11 3A11 0A11 7A11 9A11 41A11 43A11 40A11 47A11 49A11 31A11 33A11 30A11 37A11 39A11 /1A11 Peak # Ret. Time Area Area % 1 11.077 727371 50.09 2 12.931 724773 49.91 (R)-3cf 1A21 1A01 41A996 1A/1 :G 1A31 1A41 1A11 1A11 3A11 0A11 7A11 9A11 41A11 43A11 40A11 47A11 49A11 31A11 33A11 30A11 37A11 39A11 /1A11 Peak # Ret. Time Area Area % 1 10.887 12118346 100 S26

3ag: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 95/5 n-hexane/2-propanol, 0.5 ml/min, major isomer: t R = 16.2 min, minor isomer: t R = 14.9 min, UV detection at 280 nm, 30 o C). rac-3ag Peak # Ret. Time Area Area % 1 14.765 61287861 49.03 2 16.155 63704449 50.97 (R)-3ag Peak # Ret. Time Area Area % 1 14.876 5009147 11.68 2 16.221 37881591 88.32 S27

3ah: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 95/5 n-hexane/2-propanol, 0.5 ml/min, major isomer: t R = 21.9 min, minor isomer: t R = 16.7 min, UV detection at 250 nm, 30 o C). rac-3ah Peak # Ret. Time Area Area % 1 16.763 59144912 49.78 2 21.958 59671803 50.22 (R)-3ah Peak # Ret. Time Area Area % 1 16.712 11092249 9.65 2 21.890 103810610 90.35 S28

3jh: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 80/20 n-hexane/2-propanol, 0.5 ml/min, major isomer: t R = 29.6 min, minor isomer: t R = 26.0 min, UV detection at 350 nm, 30 o C). rac-3jh Peak # Ret. Time Area Area % 1 25.783 7106256 49.85 2 29.466 7149411 50.15 (R)-3jh Peak # Ret. Time Area Area % 1 25.949 290466 10.38 2 29.623 2507056 89.62 S29

3di: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 99.6/0.4 n-hexane/2-propanol, 2.5 ml/min, major isomer: t R = 7.3 min, minor isomer: t R = 5.8 min, UV detection at 350 nm, 30 o C). rac-3di Peak # Ret. Time Area Area % 1 5.306 26752846 49.89 2 6.925 26874580 50.11 (R)-3di Peak # Ret. Time Area Area % 1 5.810 737054 1.25 2 7.323 58336047 98.75 S30

3dj: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 99/1 n-hexane/2-propanol, 0.5 ml/min, major isomer: t R = 8.0 min, minor isomer: t R = 7.0 min, UV detection at 300 nm, 30 o C). rac-3dj Peak # Ret. Time Area Area % 1 7.048 41923049 49.37 2 8.655 42994920 50.63 (R)-3dj Peak # Ret. Time Area Area % 1 7.040 2359347 4.48 2 8.033 50295912 95.52 S31

3jk: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 88/12 n-hexane/2-propanol, 0.5 ml/min, major isomer: t R = 19.7 min, minor isomer: t R = 18.6 min, UV detection at 350 nm, 30 o C). rac-3jk Peak # Ret. Time Area Area % 1 18.676 3052509 49.73 2 20.351 3085234 50.27 (R)-3jk Peak # Ret. Time Area Area % 1 18.559 1733176 1.44 2 19.703 118492180 98.56 S32

3al: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 97/3 n-hexane/2-propanol, 0.5 ml/min, major isomer: t R = 12.3 min, minor isomer: t R = 9.6 min, UV detection at 270 nm, 30 o C). rac-3al Peak # Ret. Time Area Area % 1 9.698 27236090 50.25 2 13.081 26969723 49.75 (R)-3al Peak # Ret. Time Area Area % 1 9.613 2470389 7.85 2 12.301 28993815 92.15 S33

3jm: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 92/8 n-hexane/2-propanol, 0.5 ml/min, major isomer: t R = 14.8 min, minor isomer: t R = 12.0 min, UV detection at 270 nm, 30 o C). rac-3jm Peak # Ret. Time Area Area % 1 11.737 45360655 49.64 2 14.846 46026631 50.36 (R)-3jm Peak # Ret. Time Area Area % 1 12.006 1004910 1.22 2 14.842 81403127 98.78 S34

3jn: The enantiomeric ratio was determined by HPLC analysis in comparison with authentic racemic material (CHIRALCEL OD-H column, 99/1 n-hexane/2-propanol, 1.0 ml/min, major isomer: t R = 13.0 min, minor isomer: t R = 9.4 min, UV detection at 300 nm, 30 o C). rac-3jn Peak # Ret. Time Area Area % 1 9.151 56725034 49.55 2 13.084 57763402 50.45 (R)-3jn Peak # Ret. Time Area Area % 1 9.391 494690 1.19 2 13.016 40929775 98.81 S35

3jk-Bpin: The enantiomeric ratio was assigned by HPLC analysis in comparison with authentic racemic material (CHIRALPAK AD-H column, 95/5 n-hexane/2-propanol, 1.0 ml/min, major isomer: t R = 5.0 min, minor isomer: t R = 4.3 min, UV detection at 220 nm, 30 o C). The 3ik-Bpin was relatively unstable under HPLC analytical conditions, and thus the correct er value could not be determined. rac-3jk-bpin 3?11 4?21 9E 4?11 1?21 0?3B1 2?421 Peak # Ret. Time Area Area % 1 4.280 8257163 49.72 2 5.150 8350191 50.28 1?11 1?11 3?11 0?11 F?11 The absorption spectra of the peak #1 The absorption spectra of the peak #2 (R)-3jk-Bpin /@21 /@11 0@67/ 3@21 :F 3@11 4@21 4@11 0@376 Peak # Ret. Time Area Area % 1 4.269 10338447 12.33 2 4.963 73494240 87.67 1@21 1@11 1@11 3@11 0@11 7@11 S36

Characterization Data for Products 1 H, 13 C, 11 B, and 19 F MR spectra for all compounds are attached in the last part. (E)-2-(Oct-1-en-1-yl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (1a) oil; 1 H MR (400 MHz, CDCl 3 ) δ 0.90 (t, J = 6.8 Hz, 3H), 1.25-1.36 (m, 6H), 1.41-1.48 (m, 2H), 2.16-2.22 (m, 2H), 5.55 (d, J = 18.0 Hz, 1H), 5.69 (bs, 2H), 6.31 (dd, J = 0.8, 7.2 Hz, 2H), 6.36 (dt, J = 6.4, 18.0 Hz, 1H), 6.99 (dd, J = 0.8, 8.4 Hz, 2H), 7.19 (dd, J = 7.2, 8.4 Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 14.26, 22.77, 28.77, 29.05, 31.89, 36.04, 105.70, 117.50, 119.85, 127.69, 136.49, 141.42, 148.30. The carbon signal bound to the boron was not observed due to quadrupolar relaxation.; 11 B MR (128 MHz, CDCl 3 ) δ 27.22; HRMS (APCI) m/z ([M+H] + ) calcd for C 18 H 24 B 2 : 279.2030, found: 279.2030. (E)-2-(3-Phenylprop-1-en-1-yl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (1b) dark brown solid; m.p. 69-70 o C; 1 H MR (400 MHz, CDCl 3 ) δ 3.52 (d, J = 6.4 Hz, 2H), 5.58 (d, J = 18.0 Hz, 1H), 5.68 (bs, 2H), 6.27 (d, J = 7.2 Hz, 2H), 6.46 (dt, J = 6.4, 18.0 Hz, 1H), 6.99 (d, J = 8.4 Hz, 2H), 7.07 (dd, J = 7.6, 8.4 Hz, 2H), 7.19-7.25 (m, 3H), 7.32 (t, J = 7.2 Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 42.39, 105.76, 117.60, 119.88, 126.46, 127.68, 128.70, 128.99, 136.45, 139.46, 141.27, 146.05. The carbon signal bound to the boron was not observed due to quadrupolar relaxation.; 11 B MR (128 MHz, CDCl 3 ) δ 27.40; HRMS (APCI) m/z ([M+H] + ) calcd for C 19 H 18 B 2 : 285.1561, found: 285.1559. (E)-2-(3-Methylbut-1-en-1-yl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (1c) white solid; m.p. 51-53 o C; 1 H MR (400 MHz, CDCl 3 ) δ 1.06 (d, J = 6.4 Hz, 6H), 2.40 (dq, J = 6.4, 6.4 Hz, 1H), 5.51 (dd, J = 1.6, 18.0 Hz, 1H), 5.71 (bs, 2H), 6.31 (dd, J = 0.8, 7.6 Hz, 2H), 6.34 (dd, J = 6.4, 18.0 Hz, 1H), 6.99 (dd, J = 0.8, 8.4 Hz, 2H), 7.09 (dd, J = 7.6, 8.4 Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 21.91, 33.80, 105.70, 117.50, 119.90, 127.70, 136.49, 141.43, 154.69. The carbon signal bound to the boron was not observed due to quadrupolar relaxation.; 11 B MR (128 MHz, CDCl 3 ) δ 27.87; HRMS (APCI) m/z ([M+H] + ) calcd for C 15 H 18 B 2 : 237.1560, found: 237.1559. (E)-2-(2-Cyclohexylvinyl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (1d) white solid; m.p. 118-120 o C; 1 H MR (400 MHz, CDCl 3 ) δ 1.08-1.23 (m, 3H), 1.25-1.36 (m, 2H), 1.66-1.71 (m, 1H), 1.73-1.80 (m, 4H), 2.03-2.11 (m, 1H), 5.49 (dd, J = 1.2, 18.0 Hz, 1H), 5.70 (bs, 2H), 6.27-6.33 (m, 3H), 6.99 (dd, J = 0.8, 8.4 Hz, 2H), 7.09 (dd, J = 7.6, 8.4 Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ S37

26.12, 26.32, 32.47, 43.45, 105.69, 117.48, 119.86, 127.70, 136.49, 141.44, 153.59. The carbon signal bound to the boron was not observed due to quadrupolar relaxation.; 11 B MR (128 MHz, CDCl 3 ) δ 27.65; HRMS (APCI) m/z ([M+H] + ) calcd for C 18 H 22 B 2 : 277.1874, found: 277.1873. (E)-2-(3,3-Dimethylbut-1-en-1-yl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (1e) white solid; m.p. 94-95 o C; 1 H MR (400 MHz, CDCl 3 ) δ 1.07 (s, 9H), 5.47 (d, J = 18.4 Hz, 1H), 5.72 (bs, 2H), 6.31 (dd, J = 0.8, 7.6 Hz, 2H), 6.36 (d, J = 18.4 Hz, 1H), 6.99 (dd, J = 0.8, 8.4 Hz, 2H), 7.09 (dd, J = 7.6, 8.4 Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 29.18, 35.01, 105.70, 117.49, 119.86, 127.70, 136.49, 141.45, 158.25. The carbon signal bound to the boron was not observed due to quadrupolar relaxation.; 11 B MR (128 MHz, CDCl 3 ) δ 27.69; HRMS (APCI) m/z ([M+H] + ) calcd for C 16 H 20 B 2 : 251.1717, found: 251.1715. (E)-2-(6-Cyclohex-1-en-1-yl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (1f) oil; 1 H MR (400 MHz, CDCl 3 ) δ 1.59 (dt, J = 7.6, 18.0 Hz, 2H), 1.76-1.83 (m, 2H), 2.18-2.23 (m, 2H), 3.55 (t, J = 6.8 Hz, 2H), 5.55 (d, J = 18.0 Hz, 1H), 5.68 (bs, 2H), 6.26-6.34 (m, 3H), 6.99 (dd, J = 0.8, 8.4 Hz, 2H), 7.09 (t, J = 7.6, 8.4 Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 25.89, 32.12, 35.04, 45.03, 105.74, 117.56, 119.85, 127.68, 136.45, 141.30, 146.97. The carbon signal bound to the boron was not observed due to quadrupolar relaxation.; 11 B MR (128 MHz, CDCl 3 ) δ 27.22; HRMS (APCI) m/z ([M+H] + ) calcd for C 16 H 19 BCl 2 : 285.1327, found: 285.1325. (E)-2-Styryl-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (1g) yellow solid; m.p. 105-106 o C; 1 H MR (400 MHz, CDCl 3 ) δ 5.85 (bs, 2H), 6.32 (d, J = 18.4 Hz, 1H), 6.36 (dd, J = 0.8, 7.2 Hz, 2H), 7.02 (dd, J = 0.8, 8.4 Hz, 2H), 7.10-7.17 (m, 3H), 7.31 (t, J = 7.2 Hz, 1H), 7.38 (t, J = 7.2 Hz, 2H), 7.51 (d, J = 7.2 Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 105.93, 117.77, 120.01, 126.93, 127.74, 128.84 (2C), 136.51, 137.69, 141.26, 143.82. The carbon signal bound to the boron was not observed due to quadrupolar relaxation.; 11 B MR (128 MHz, CDCl 3 ) δ 28.08; HRMS (APCI) m/z ([M+H] + ) calcd for C 18 H 16 B 2 : 271.1404, found: 271.1405. (E)-2-(4-Fluorostyryl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (1h) yellow solid; 143 o C- decomposition; 1 H MR (400 MHz, CDCl 3 ) δ 5.83 (bs, 2H), 6.22 (d, J = 18.4 Hz, 1H), 6.36 (dd, J = 0.8, 7.2 Hz, 2H), 7.02-7.14 (m, 7H), 7.45-7.49 (m, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 105.95, 115.82 (d, J = 21.7 Hz), 117.83, 120.01, 127.74, 128.53 (d, J = 8.2 Hz), 133.93, 136.52, 141.21, 142.52, S38

163.15 (d, J = 245.9 Hz). The carbon signal bound to the boron was not observed due to quadrupolar relaxation.; 11 B MR (128 MHz, CDCl 3 ) δ 27.87; 19 F MR (376 MHz, CDCl 3 ) δ -112.68; HRMS (APCI) m/z ([M+H] + ) calcd for C 18 H 15 BF 2 : 289.1310, found: 289.1301. (E)-2-(4-(Trifluoromethyl)styryl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (1i) yellow solid; 171 o C- decomposition; 1 H MR (400 MHz, CDCl 3 ) δ 5.84 (bs, 2H), 6.37 (dd, J = 0.8, 7.6 Hz, 2H), 6.41 (d, J = 18.4 Hz, 1H), 7.04 (dd, J = 0.8, 7.6 Hz, 2H), 7.12 (t, J = 7.6 Hz, 2H), 7.15 (d, J = 18.4 Hz, 1H), 7.58 (d, J = 8.4 Hz, 2H), 7.62 (d, J = 8.4 Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 106.07, 117.99, 120.09, 124.25 (q, J = 270.4 Hz), 125.79 (q, J = 3.7 Hz), 125.19, 127.02, 127.75, 130.39 (q, J = 32.2 Hz), 136.50, 141.03, 142.09. The carbon signal bound to the boron was not observed due to quadrupolar relaxation.; 11 B MR (128 MHz, CDCl 3 ) δ 27.80; 19 F MR (376 MHz, CDCl 3 ) δ -62.55; HRMS (APCI) m/z ([M+H] + ) calcd for C 19 H 15 BF 3 2 : 339.1278, found: 339.1289. (E)-2-(4-Methoxystyryl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (1j) yellow solid; 193 o C- decomposition; 1 H MR (400 MHz, CDCl 3 ) δ 3.83 (s, 3H), 5.83 (bs, 2H), 6.16 (d, J = 18.4 Hz, 1H), 6.36 (dd, J = 0.8, 7.2 Hz, 2H), 6.90 (d, J = 8.4 Hz, 2H), 7.02 (dd, J = 0.8, 8.4 Hz, 2H), 7.08-7.13 (m, 3H), 7.45 (d, J = 8.4 Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 55.49, 108.84, 114.25, 117.66, 119.95, 127.73, 128.27, 130.59, 136.52, 141.37, 143.35, 160.28. The carbon signal bound to the boron was not observed due to quadrupolar relaxation.; 11 B MR (128 MHz, CDCl 3 ) δ 28.38; HRMS (APCI) m/z ([M+H] + ) calcd for C 19 H 18 B 2 O: 301.1510, found: 301.1499. 2-(1-Phenylvinyl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (1k) white solid; m.p. 90-91 o C; 1 H MR (400 MHz, CDCl 3 ) δ 5.72-5.80 (m, 3H), 5.88 (d, J = 2.0 Hz, 1H), 6.31 (dd, J = 0.8, 6.4 Hz, 2H), 7.03 (dd, J = 0.8, 8.4 Hz, 2H), 7.10 (dd, J = 7.2, 8.4 Hz, 2H), 7.29-7.41 (m, 5H); 13 C MR (100 MHz, CDCl 3 ) δ 106.09, 117.94, 120.04, 125.09, 127.51, 127.66, 127.72, 128.83, 136.48, 141.12, 142.29. The carbon signal bound to the boron was not observed due to quadrupolar relaxation.; 11 B MR (128 MHz, CDCl 3 ) δ 28.85; HRMS (APCI) m/z ([M+H] + ) calcd for C 18 H 16 B 2 : 271.1404, found: 271.1399. 4-(1-(1H-aphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)octyl)morpholine (3aa) oil; 1 H MR (400 MHz, benzene-d 6 ) δ 0.88 (t, J = 6.4 Hz, 3H), 1.21-1.44 (m, 11H), 1.48-1.60 (m, 2H), 2.19-2.22 (m, 2H), 2.37-2.40 (m, 2H), 3.59-3.70 (m, 4H), 5.62 (bs, 2H), 6.03 (dd, J = 2.4, 6.0 Hz, 2H), 7.02-7.07 (m, 4H); S39

13 C MR (100 MHz, benzene-d 6 ) δ 13.99, 22.71, 27.14, 28.97, 29.25, 30.40, 31.99, 53.81, 57.53 (the boron-bound carbon, very weak), 67.12, 105.91, 117.93, 120.28, 127.54, 136.75, 140.87; 11 B MR (128 MHz, benzene-d 6 ) δ 30.91; HRMS (APCI) m/z ([M+H] + ) calcd for C 22 H 33 B 3 O: 366.2715, found: 366.2715. 4-(1-(1H-aphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)-3-phenylpropyl)morpholine (3ba) white solid; m.p. 56-58 o C; 1 H MR (400 MHz, benzene-d 6 ) δ 1.51 (dd, J = 4.4, 9.2 Hz, 1H), 1.57-1.67 (m, 1H), 1.82-1.87 (m, 1H), 2.14-2.18 (m, 2H), 2.30-2.34 (m, 2H), 2.39-2.46 (m, 1H), 2.57-2.64 (m, 1H), 3.56-3.67 (m, 4H), 5.48 (bs, 2H), 6.02 (dd, J = 2.0, 6.4 Hz, 2H), 7.01-7.04 (m, 2H), 7.06-7.10 (m, 4H), 7.15-7.18 (m, 3H); 13 C MR (100 MHz, benzene-d 6 ) δ 30.99, 33.68, 53.98, 57.30 (the boron-bound carbon, very weak), 67.45, 106.35, 118.40, 120.69, 126.27, 127.93, 128.65, 128.72, 137.13, 141.17, 142.58; 11 B MR (128 MHz, benzene-d 6 ) δ 30.57; HRMS (APCI) m/z ([M+H] + ) calcd for C 23 H 27 B 3 O: 372.2246, found: 372.2254. 4-(3-Methyl-1-(1H-naphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)butyl)morpholine (3ca) white solid; m.p. 144-146 o C; 1 H MR (400 MHz, benzene-d 6 ) δ 0.80 (d, J = 6.4 Hz, 3H), 0.83 (d, J = 6.4 Hz, 3H), 1.20 1.27 (m, 1H), 1.36-1.43 (m, 1H), 1.46-1.56 (m, 1H), 1.61 (dd, J = 5.2, 10.0 Hz, 1H), 2.16-2.20 (m, 2H), 2.35-2.40 (m, 2H), 3.58-3.67 (m, 4H), 5.53 (bs, 2H), 6.00 (dd, J = 1.6, 6.8 Hz, 2H), 7.02-7.09 (m, 4H); 13 C MR (100 MHz, benzene-d 6 ) δ 22.66, 24.41, 26.92, 38.43, 54.00, 67.59, 106.30, 118.33, 120.64, 127.91, 137.11, 141.21. The carbon signal bound to the boron was not observed due to quadrupolar relaxation.; 11 B MR (128 MHz, benzene-d 6 ) δ 31.24; HRMS (APCI) m/z ([M+H] + ) calcd for C 19 H 27 B 3 O: 324.2245, found: 324.2249. 4-(2-Cyclohexyl-1-(1H-naphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)ethyl)morpholine (3da) white solid; 57 o C- decomposition; 1 H MR (400 MHz, benzene-d 6 ) δ 0.72-0.92 (m, 2H), 0.99-1.15 (m, 3H), 1.19-1.29 (m, 2H), 1.15-1.51 (m, 1H), 1.57-1.68 (m, 6H), 2.18-2.23 (m, 2H), 2.37-2.42 (m, 2H), 3.59-3.68 (m, 4H), 5.56 (bs, 2H), 6.01(dd, J = 2.0, 6.4 Hz, 2H), 7.02-7.08 (m, 4H); 13 C MR (100 MHz, benzene-d 6 ) δ 26.43, 26.51, 26.90, 33.84, 34.99, 36.66, 36.73, 53.97, 67.61, 106.27, 118.35, 120.62, 127.92, 137.14, 141.23. The carbon signal bound to the boron was not observed due to quadrupolar relaxation.; 11 B MR (128 MHz, benzene-d 6 ) δ 30.74; HRMS (APCI) m/z ([M+H] + ) calcd for C 22 H 31 B 3 O: 364.2559, found: 364.2558. S40

4-(3,3-Dimethyl-1-(1H-naphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)butyl)morpholine (3ea) white solid; 153 o C- decomposition; 1 H MR (400 MHz, benzene-d 6 ) δ 0.85 (s, 9H), 1.27 (dd, J = 9.6, 14.0 Hz, 1H), 1.50 (dd, J = 2.4, 14.0 Hz, 1H), 1.64 (dd, J = 2.4, 9.6 Hz, 1H), 2.18-2.23 (m, 2H), 2.38-2.43 (m, 2H), 3.57-3.66 (m, 4H), 5.52 (bs, 2H), 6.04 (dd, J = 1.6, 6.0 Hz, 2H), 7.03-7.09 (m, 4H); 13 C MR (100 MHz, benzene-d 6 ) δ 30.20, 30.42, 41.19, 53.40, 67.70, 106.25, 118.33, 120.52, 127.93, 137.12, 141.25. The carbon signal bound to the boron was not observed due to quadrupolar relaxation.; 11 B MR (128 MHz, benzene-d 6 ) δ 31.22; HRMS (APCI) m/z ([M+H] + ) calcd for C 20 H 29 B 3 O: 338.2402, found: 338.2405. 4-(6-Chloro-1-(1H-naphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)hexyl)morpholine (3fa) white solid; 56 o C- decomposition; 1 H MR (400 MHz, benzene-d 6 ) δ 0.97-1.46 (m, 9H), 2.16-2.19 (m, 2H), 2.32-2.36 (m, 2H), 3.08 (t, J = 6.4 Hz, 2H), 3.59-3.69 (m, 4H), 5.50 (bs, 2H), 6.03 (dd, J = 2.4, 6.0 Hz, 2H), 7.02-7.07 (m, 4H); 13 C MR (100 MHz, benzene-d 6 ) δ 26.57, 27.69, 29.14, 32.56, 45.02, 54.17, 57.68 (the boron-bound carbon, very weak), 67.49, 106.29, 118.42, 120.62, 128.18, 137.12, 141.11; 11 B MR (128 MHz, benzene-d 6 ) δ 31.57; HRMS (APCI) m/z ([M+H] + ) calcd for C 20 H 28 BCl 3 O: 372.2012, found: 372.2011. 4-(1-(1H-aphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)-2-phenylethyl)morphorline (3ga) white solid; 133 o C- decomposition; 1 H MR (400 MHz, benzene-d 6 ) δ 1.91 (dd, J = 5.2, 10.8 Hz, 1H), 2.18-2.23 (m, 2H), 2.37-2.44 (m, 3H), 2.88 (dd, J = 5.2, 12.8 Hz, 1H), 3.57-3.67 (m, 4H), 5.36 (bs, 2H), 5.91 (dd, J = 2.0, 6.4 Hz, 2H), 6.98-7.05 (m, 9H); 13 C MR (100 MHz, benzene-d 6 ) δ 34.32, 53.45, 58.98 (the boron-bound carbon, very weak), 67.56, 106.11, 118.22, 120.48, 126.50, 127.88, 128.73, 129.52, 137.07, 140.50, 141.17; 11 B MR (128 MHz, benzene-d 6 ) δ 31.62; HRMS (APCI) m/z ([M+H] + ) calcd for C 22 H 25 B 3 O: 358.2089, found: 358.2102. 4-(2-(4-Fluorophenyl)-1-(1H-naphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)ethyl)morpholine (3ha) white solid; 61 o C- decomposition; 1 H MR (400 MHz, benzene-d 6 ) δ 1.73 (dd, J = 5.2, 10.8 Hz, 1H), 2.15-2.20 (m, 2H), 2.29 (dd, J = 10.8, 12.8 Hz, 1H), 2.34-2.39 (m, 2H), 2.74 (dd, J = 5.2, 12.8 Hz, 1H), 3.57-3.67 (m, 4H), 5.25 (bs, 2H), 5.90 (dd, J = 1.6, 6.4 Hz, 2H), 6.66-6.71 (m, 2H), 6.75-6.79 (m, 2H), 6.99-7.05 (m, 4H); 13 C MR (100 MHz, benzene-d 6 ) δ 33.83, 53.63, 59.33 (the boron-bound carbon, very weak), 67.49, 106.15, 115.41 (d, J = 21.0 Hz), 118.34, 120.44, 127.93, 130.95 (d, J = 7.5 Hz), 135.96 (d, J = 3.0 Hz), 137.04, 141.02, 161.88 (d, J = 242.7 Hz); 11 B MR (128 MHz, S41

benzene-d 6 ) δ 30.65; 19 F MR (376 MHz, benzene-d 6 ) δ -116.51; HRMS (APCI) m/z ([M+H] + ) calcd for C 22 H 24 BF 3 O: 376.1995, found: 376.1995. 4-(1-(1H-aphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)-2-(4-(trifluoromethyl)phenyl)ethyl)morph oline (3ia) white solid; 147 o C- decomposition; 1 H MR (400 MHz, benzene-d 6 ) δ 1.68 (dd, J = 5.2, 10.4 Hz, 1H), 2.13-2.18 (m, 2H), 2.26 (m, 3H), 2.70 (dd, J = 5.2, 12.8 Hz, 1H), 3.55-3.66 (m, 4H), 5.19 (bs, 2H), 5.89 (dd, J = 2.0, 6.4 Hz, 2H), 6.84, (d, J = 8.0 Hz, 2H), 6.98-7.04 (m, 4H), 7.22 (d, J = 8.0 Hz, 2H); 13 C MR (100 MHz, benzene-d 6 ) δ 34.66, 53.69, 59.12 (the boron-bound carbon, very weak), 67.44, 106.19, 118.52, 120.44, 125.07 (q, J = 270.3 Hz), 125.49 (q, J = 3.7 Hz), 127.92, 128.75 (q, J = 32.1 Hz), 129.86, 137.04, 140.81, 144.68; 11 B MR (128 MHz, benzene-d 6 ) δ 31.06; 19 F MR (376 MHz, benzene-d 6 ) δ -61.97; HRMS (APCI) m/z ([M+H] + ) calcd for C 23 H 24 BF 3 3 O: 426.1963, found: 426.1963. 4-(2-(1H-aphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)-1-(4-(trifluoromethyl)phenyl)ethyl)morp holine (3ia ) white solid; 159 o C- decomposition; 1 H MR (400 MHz, benzene-d 6 ) δ 0.68 (dd, J = 5.6, 16.0 Hz, 1H), 0.95 (dd, J = 8.4, 16.0 Hz, 1H), 1.95-2.06 (m, 4H), 3.18 (dd, J = 5.6, 8.4 Hz, 1H), 3.48-3.57 (m, 4H), 5.99 (bs, 2H), 6.14 (dd, J = 2.8, 5.8 Hz, 2H), 6.92 (d, J = 8.0 Hz, 2H), 7.10-7.13 (m, 4H), 7.33 (d, J = 8.0 Hz, 2H); 13 C MR (100 MHz, benzene-d 6 ) δ 18.10 (the boron-bound carbon, very weak), 50.52, 67.04, 67.39, 106.00, 118.21, 120.58, 125.00 (q, J = 3.7 Hz), 125.42 (q, J = 270.3 Hz), 127.94, 128.60, 129.64 (q, J = 32.2 Hz), 137.26, 141.49, 145.44; 11 B MR (128 MHz, benzene-d 6 ) δ 31.15; 19 F MR (376 MHz, benzene-d 6 ) δ -62.01; HRMS (APCI) m/z ([M+H] + ) calcd for C 23 H 24 BF 3 3 O: 426.1963, found: 426.1962. 2-(1-(Piperidin-1-yl)octyl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (3ab) oil; 1 H MR (400 MHz, benzene-d 6 ) δ 0.88 (t, J = 6.8 Hz, 3H), 1.20-1.30 (m, 9H), 1.36-1.44 (m, 3H), 1.48-1.59 (m, 5H), 1.60-1.69 (m, 2H), 2.22-2.36 (m, 2H), 2.42-2.56 (m, 2H), 5.67 (bs, 2H), 6.02 (dd, J = 2.0, 6.4 Hz, 2H), 7.02-7.08 (m, 4H); 13 C MR (100 MHz, benzene-d 6 ) δ 14.38, 23.10, 25.19, 26.95, 27.94, 29.42, 29.66, 30.82, 32.38, 54.66, 58.11 (the boron-bound carbon, very weak), 106.24, 118.11, 120.68, 127.91, 137.17, 141.48; 11 B MR (128 MHz, benzene-d 6 ) δ 31.18; HRMS (APCI) m/z ([M+H] + ) calcd for C 23 H 35 B 3 : 364.2923, found: 364.2922. 2-(1-(2,2,6,6-Tetramethylpiperidin-1-yl)octyl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborini S42

ne (3ac) white solid; m.p. 96-98 o C; 1 H MR (400 MHz, benzene-d 6 ) δ 0.94 (t, J = 6.4 Hz, 3H), 1.15-1.21 (m, 13H), 1.24-1.36 (m, 9H), 1.39-1.43 (m, 4H), 1.47-1.60 (m, 3H), 1.77-1.84 (m, 1H), 2.60 (d, J = 10.0 Hz, 1H), 5.71 (bs, 2H), 6.16 (dd, J = 2.0, 6.4 Hz, 2H), 7.07-7.13 (m, 4H); 13 C MR (100 MHz, benzene-d 6 ) δ 14.42, 18.69, 23.12, 29.79, 30.72, 30.74, 32.33, 34.14, 44.20, 55.96, 106.01, 117.95, 120.24, 128.00, 137.26, 141.72 (Some signals merge.); 11 B MR (128 MHz, benzene-d 6 ) δ 33.69; HRMS (APCI) m/z ([M+H] + ) calcd for C 27 H 43 B 3 : 420.3549, found: 420.3549. 2-(1-(Azepan-1-yl)-2-(4-methoxyphenyl)ethyl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborini ne (3jd) oil; 1 H MR (400 MHz, benzene-d 6 ) δ 1.54-1.63 (m, 8H), 2.46-2.56 (m, 4H), 2.64-2.70 (m, 2H), 2.90-2.97 (m, 1H), 3.33 (s, 3H), 5.70 (bs, 2H), 6.03 (dd, J = 1.6, 6.8 Hz, 2H), 6.77-6.80 (m, 2H), 6.99-7.07 (m, 6H); 13 C MR (100 MHz, benzene-d 6 ) δ 27.31, 30.27, 31.69, 54.86, 55.38, 106.06, 114.47, 117.99, 120.50, 127.95, 130.25, 133.31, 137.18, 141.57, 158.75. The carbon signal bound to boron was not observed due to quadrupolar relaxation.; 11 B MR (128 MHz, benzene-d 6 ) δ 32.37; HRMS (APCI) m/z ([M+H] + ) calcd for C 25 H 31 B 3 O: 400.2559, found: 400.2558. tert-butyl 4-(1-(1H-naphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)octyl)piperazine-1-carboxylate (3ae) oil; 1 H MR (400 MHz, benzene-d 6 ) δ 0.87 (t, J = 6.8 Hz, 3H), 1.19-1.28 (m, 10H), 1.31-1.40 (m, 2H), 1.49-1.56 (m, 10H), 2.08-2.20 (m, 2H), 2.24-2.42 (m, 2H), 3.41-3.59 (m, 4H), 5.72 (bs, 2H), 6.08 (dd, J = 2.0, 6.4 Hz, 2H), 7.05-7.07 (m, 4H); 13 C MR (100 MHz, benzene-d 6 ) δ 14.37, 23.08, 27.66, 28.56, 29.37, 29.61, 30.71, 32.35, 44.71 (the boron-bound carbon, very weak), 53.11, 57.19, 79.21, 106.27, 118.24, 120.67, 127.91, 137.11, 141.34, 154.74; 11 B MR (128 MHz, benzene-d 6 ) δ 28.56; HRMS (APCI) m/z ([M+H] + ) calcd for C 27 H 42 B 4 O 2 : 465.3400, found: 465.3400. 8-(3-Methyl-1-(1H-naphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)butyl)-1,4-dioxa-8-azaspiro[4.5] decane (3cf) white solid; 169 o C- decomposition; 1 H MR (400 MHz, benzene-d 6 ) δ 0.81 (d, J = 6.4 Hz, 3H), 0.84 (d, J = 6.4 Hz, 3H), 1.26-1.32 (m, 1H), 1.45-1.55 (m, 2H), 1.78-1.90 (m, 5H), 2.50-2.56 (m, 2H), 2.71-2.77 (m, 2H), 3.55 (s, 4H), 5.72 (bs, 2H), 6.04 (dd, J = 2.0, 6.0 Hz, 2H), 7.02-7.08 (m, 4H) ; 13 C MR (100 MHz, benzene-d 6 ) δ 22.70, 24.18, 27.19, 36.19, 38.37, 51.04, 64.24, 106.31, 107.54, 118.20, 127.93, 137.14, 141.37. The carbon signal bound to boron was not observed due to quadrupolar relaxation.; 11 B MR (128 MHz, benzene-d 6 ) δ 31.69; HRMS (APCI) m/z ([M+H] + ) calcd for C 22 H 31 B 3 O: 380.2508, found: 380.2514. S43

2-(1-(3,4-Dihydroisoquinolin-2(1H)yl)octyl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (3ag) oil; 1 H MR (400 MHz, benzene-d 6 ) δ 0.89 (t, J = 6.8 Hz, 3H), 1.24-1.33 (m, 9H), 1.37-1.46 (m, 1H), 1.50-1.59 (m, 1H), 1.64-1.71 (m, 1H), 1.78 (dd, J = 4.4, 9.2 Hz, 1H), 2.55-2.73 (m, 3H), 2.79-2.86 (m, 1H), 3.55 (d, J = 14.8 Hz, 1H), 3.81 (d, J = 14.8 Hz, 1H), 5.66 (bs, 2H), 6.00 (dd, J = 1.6, 6.8 Hz, 2H), 6.88 (d, J = 2.0, 6.8 Hz, 1H), 7.01-7.10 (m, 7H); 13 C MR (100 MHz, benzene-d 6 ) δ 14.39, 23.10, 27.70, 29.62, 29.66, 29.84, 30.82, 32.37, 51.07, 56.12, 56.58 (the boron-bound carbon, very weak), 106.32, 118.25, 120.69, 126.01, 126.48, 127.07, 127.92, 128.95, 135.00, 135.82, 137.14, 141.33; 11 B MR (128 MHz, benzene-d 6 ) δ 30.51; HRMS (APCI) m/z ([M+H] + ) calcd for C 27 H 35 B 3 : 412.2923, found: 412.2923. 5-(1-(1H-aphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)octyl-4,5,6,7-tetrahydrothieno[3,2-c]pyrid ine (3ah) oil; 1 H MR (400 MHz, benzene-d 6 ) δ 0.89 (t, J = 6.8 Hz, 3H), 1.73-1.30 (m, 9H), 1.35-1.41 (m, 1H), 1.43-1.55 (m, 1H), 1.58-1.66 (m, 1H), 1.80 (dd, J = 4.8, 9.2 Hz, 1H), 2.53-2.64 (m, 3H), 2.70-2.77 (m, 1H), 3.41 (d, J = 14.4 Hz, 1H), 3.69 (dd, J = 14.4 Hz, 1H), 5.62 (bs, 2H), 5.99 (dd, J = 2.0, 6.4 Hz, 2H), 6.55 (d, J = 5.2 Hz, 1H), 6.84 (d, J = 5.2 Hz, 1H), 7.01-7.06 (m, 4H); 13 C MR (100 MHz, benzene-d 6 ) δ 14.39, 23.10, 26.10, 27.75, 29.65 (2C), 30.80, 32.36, 50.99, 52.84, 55.85 (the boron-bound carbon, very weak), 106.31, 118.27, 120.67, 122.89, 125.70, 127.92, 133.82, 134.84, 137.13, 141.28; 11 B MR (128 MHz, benzene-d 6 ) δ 30.81; HRMS (APCI) m/z ([M+H] + ) calcd for C 25 H 33 B 3 S: 418.2487, found: 418.2487. 5-(2-(4-Methoxyphenyl)-1-(1H-naphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)rthyl)-4,5,6,7-tetrah ydrothieno[3,2-c]pyridine (3jh) white solid; 119 o C- decomposition; 1 H MR (400 MHz, benzene-d 6 ) δ 2.28 (dd, J = 5.2, 10.8 Hz, 1H), 2.45-2.51 (m, 2H), 2.58-2.74 (m, 3H), 2.93 (dd, J = 5.2, 13.2 Hz, 1H), 3.30 (s, 3H), 3.45 (d, J = 14.0 Hz, 1H), 3.72 (d, J = 14.0 Hz, 1H), 5.53 (bs, 2H), 5.89 (dd, J = 1.6, 6.8 Hz, 2H), 6.56 (d, J = 5.2 Hz, 1H), 6.71-6.75 (m, 2H), 6.86 (d, J = 5.2 Hz, 1H), 6.98-7.05 (m, 6H); 13 C MR (100 MHz, benzene-d 6 ) δ 26.43, 32.85, 50.16, 52.10, 54.85, 106.17, 114.37, 118.13, 120.52, 122.92, 125.67, 127.92, 130.40, 132.43, 133.68, 135.00, 137.09, 141.32, 158.78. The carbon signal bound to boron was not observed due to quadrupolar relaxation.; 11 B MR (128 MHz, benzene-d 6 ) δ 32.12; HRMS (APCI) m/z ([M+H] + ) calcd for C 26 H 27 B 3 OS: 440.1967, found: 440.1969. 2-Cyclohexyl-,-diethyl-1-(1H-naphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)ethan-1-amine (3di) oil ; 1 H MR (400 MHz, benzene-d 6 ) δ 0.75-0.91 (m, 2H), 0.98 (t, J = 7.2 Hz, 6H), 1.13-1.22 (m, S44

5H), 1.38-1.48 (m, 1H), 1.63-1.66 (m, 4H), 1.72-1.75 (m, 1H), 2.28 (dd, J = 4.4, 9.6 Hz, 1H), 2.44 (q, J = 13.2 Hz, 2H), 2.46 (q, J = 13.2 Hz, 2H), 5.76 (bs, 2H), 6.05 (dd, J = 1.6, 6.4 Hz, 2H), 7.03-7.09 (m, 4H); 13 C MR (100 MHz, benzene-d 6 ) δ 13.53, 26.59, 26.73, 26.97, 33.77, 34.32, 34.99, 36.94, 45.68, 106.15, 118.12, 120.62, 127.96, 137.21, 141.56. The carbon signal bound to the boron was not observed due to quadrupolar relaxation.; 11 B MR (128 MHz, benzene-d 6 ) δ 32.61; HRMS (APCI) m/z ([M+H] + ) calcd for C 22 H 33 B 3 : 350.2766, found: 350.2775. -Benyl-2-cyclohexyl--methyl-1-(1H-naphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)ethan-1-ami ne (3dj) oil; 1 H MR (400 MHz, benzene-d 6 ) δ 0.78 (m, 2H), 1.12-1.18 (m, 3H), 1.22-1.29 (m, 2H), 1.53-1.73 (m, 6H), 2.05 (dd, J = 4.8, 8.8 Hz, 1H), 2.12 (s, 3H), 3.44 (d, J = 13.2 Hz, 1H), 3.49 (d, J = 13.2 Hz, 1H), 5.65 (bs, 2H), 6.05 (dd, J = 2.0, 6.4 Hz, 2H), 7.03-7.09 (m, 4H), 7.14 (t, J = 7.2 Hz, 1H), 7.24 (t, J = 7.2 Hz, 2H), 7.37 (d, J = 7.2 Hz, 2H); 13 C MR (100 MHz, benzene-d 6 ) δ 26.58, 26.66, 26.97, 33.90, 34.79, 35.49, 36.84, 40.72, 61.53, 106.26, 118.25, 120.64, 127.30, 127.94, 128.62, 129.18, 137.17, 140.56, 141.36. The carbon signal bound to boron was not observed due to quadrupolar relaxation.; 11 B MR (128 MHz, benzene-d 6 ) δ 30.65; HRMS (APCI) m/z ([M+H] + ) calcd for C 26 H 33 B 3 : 398.2767, found: 398.2769.,-Dibenzyl-2-(4-methoxyphenyl)-1-(1H-naphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)ethan-1- amine (3jk) white solid; 144 o C- decomposition; 1 H MR (400 MHz, benzene-d 6 ) δ 2.42 (dd, J = 11.6, 13.2 Hz, 1H), 2.86 (dd, J = 4.4, 11.6 Hz, 1H), 3.07 (dd, J = 4.4, 13.2 Hz, 1H), 3.31 (s, 3H), 3.45 (d, J = 14.0 Hz, 2H), 3.80 (d, J = 14.0 Hz, 2H), 5.77 (bs, 2H), 6.05 (dd, J = 1.2, 6.8 Hz, 2H), 6.73 (d, J = 8.8 Hz, 2H), 6.94-7.05 (m, 6H), 7.14 (t, J = 7.2 Hz, 2H), 7.25 (t, J = 7.2 Hz, 4H), 7.42 (d, J = 7.2 Hz, 4H); 13 C MR (100 MHz, benzene-d 6 ) δ 29.05, 49.82 (the boron-bound carbon, very weak), 54.86, 56.22, 106.12, 114.60, 118.03, 120.50, 127.47, 127.91, 128.83, 128.91, 130.11, 133.02, 137.06, 140.57, 141.42, 158.80; 11 B MR (128 MHz, benzene-d 6 ) δ 32.45; HRMS (APCI) m/z ([M+H] + ) calcd for C 33 H 33 B 3 O: 498.2717, found: 498.2719.,-Diisopropyl-1-(1H-naphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)octan-1-amine (3al) oil; 1 H MR (400 MHz, benzene-d 6 ) δ 0.92 (t, J = 6.8 Hz, 3H), 0.89 (d, J = 6.4 Hz, 6H), 1.03 (t, J = 6.4 Hz, 6H), 1.25-1.34 (m, 10H), 1.42-1.51 (m, 1H), 1.56-1.64 (m, 1H), 2.28 (dd, J = 4.0, 10.0 Hz, 1H), 2.93-3.03 (m, 2H), 5.67 (bs, 2H), 6.10 (dd, J = 2.0, 6.4 Hz, 2H), 7.05-7.11 (m, 4H); 13 C MR (100 MHz, benzene-d 6 ) δ 14.42, 22.79, 23.15, 29.08, 29.77, 30.80, 31.99, 32.35, 45.34 (the boron-bound S45