Supporting Information

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1 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 , Japan 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

2 atmosphere unless otherwise noted. S2

3 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

4 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

5 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

6 2. Cu-Catalyzed onenantioselective Hydroamination of Alkenyl dan Boronates Synthesis of 3aa (Scheme 2): Cu(OAc) 2 (4.5 mg, mmol), 1,2-bis[bis{3,5-di(trifluromethyl)phynyl}phosphino]benzene (CF 3 -dppbz, 25 mg, 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, mmol), (R)-DTBM-SEGPHOS (30 mg, 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

7 ,-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

8 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, 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

9 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

10 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

11 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 ). 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

12 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 % (R)-3aa Peak # Ret. Time Area Area % S12

13 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 % (R)-3ba Peak # Ret. Time Area Area % S13

14 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 % (R)-3ca Peak # Ret. Time Area Area % S14

15 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 % (R)-3da Peak # Ret. Time Area Area % S15

16 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 % (R)-3ea Peak # Ret. Time Area Area % S16

17 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 % (R)-3fa Peak # Ret. Time Area Area % S17

18 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 % (R)-3ga Peak # Ret. Time Area Area % S18

19 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 % (R)-3ha Peak # Ret. Time Area Area % S19

20 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 % (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 % S20

21 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 % 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 % S21

22 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 % (R)-3ab Peak # Ret. Time Area Area % S22

23 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 % (R)-3ac Peak # Ret. Time Area Area % S23

24 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 % (R)-3jd Peak # Ret. Time Area Area % S24

25 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 % (R)-3ae Peak # Ret. Time Area Area % S25

26 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 % (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 % S26

27 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 % (R)-3ag Peak # Ret. Time Area Area % S27

28 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 % (R)-3ah Peak # Ret. Time Area Area % S28

29 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 % (R)-3jh Peak # Ret. Time Area Area % S29

30 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 % (R)-3di Peak # Ret. Time Area Area % S30

31 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 % (R)-3dj Peak # Ret. Time Area Area % S31

32 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 % (R)-3jk Peak # Ret. Time Area Area % S32

33 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 % (R)-3al Peak # Ret. Time Area Area % S33

34 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 % (R)-3jm Peak # Ret. Time Area Area % S34

35 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 % (R)-3jn Peak # Ret. Time Area Area % S35

36 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 % ?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 % @21 1@11 1@11 3@11 0@11 7@11 S36

37 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), (m, 6H), (m, 2H), (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, , , , , , , 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 : , found: (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 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), (m, 3H), 7.32 (t, J = 7.2 Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 42.39, , , , , , , , , , , 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 : , found: (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 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, , , , , , , 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 : , found: (E)-2-(2-Cyclohexylvinyl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (1d) white solid; m.p o C; 1 H MR (400 MHz, CDCl 3 ) δ (m, 3H), (m, 2H), (m, 1H), (m, 4H), (m, 1H), 5.49 (dd, J = 1.2, 18.0 Hz, 1H), 5.70 (bs, 2H), (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

38 26.12, 26.32, 32.47, 43.45, , , , , , , 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 : , found: (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 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, , , , , , , 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 : , found: (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), (m, 2H), (m, 2H), 3.55 (t, J = 6.8 Hz, 2H), 5.55 (d, J = 18.0 Hz, 1H), 5.68 (bs, 2H), (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, , , , , , , 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 : , found: (E)-2-Styryl-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (1g) yellow solid; m.p 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), (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 , , , , , (2C), , , , 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 : , found: (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), (m, 7H), (m, 2H); 13 C MR (100 MHz, CDCl 3 ) δ , (d, J = 21.7 Hz), , , , (d, J = 8.2 Hz), , , , , S38

39 (d, J = 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 ; HRMS (APCI) m/z ([M+H] + ) calcd for C 18 H 15 BF 2 : , found: (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 , , , (q, J = Hz), (q, J = 3.7 Hz), , , , (q, J = 32.2 Hz), , , 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 ; HRMS (APCI) m/z ([M+H] + ) calcd for C 19 H 15 BF 3 2 : , found: (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), (m, 3H), 7.45 (d, J = 8.4 Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 55.49, , , , , , , , , , , 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: , found: (1-Phenylvinyl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (1k) white solid; m.p o C; 1 H MR (400 MHz, CDCl 3 ) δ (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), (m, 5H); 13 C MR (100 MHz, CDCl 3 ) δ , , , , , , , , , , 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 : , found: (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), (m, 11H), (m, 2H), (m, 2H), (m, 2H), (m, 4H), 5.62 (bs, 2H), 6.03 (dd, J = 2.4, 6.0 Hz, 2H), (m, 4H); S39

40 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, (the boron-bound carbon, very weak), 67.12, , , , , , ; 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: , found: (1-(1H-aphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)-3-phenylpropyl)morpholine (3ba) white solid; m.p o C; 1 H MR (400 MHz, benzene-d 6 ) δ 1.51 (dd, J = 4.4, 9.2 Hz, 1H), (m, 1H), (m, 1H), (m, 2H), (m, 2H), (m, 1H), (m, 1H), (m, 4H), 5.48 (bs, 2H), 6.02 (dd, J = 2.0, 6.4 Hz, 2H), (m, 2H), (m, 4H), (m, 3H); 13 C MR (100 MHz, benzene-d 6 ) δ 30.99, 33.68, 53.98, (the boron-bound carbon, very weak), 67.45, , , , , , , , , , ; 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: , found: (3-Methyl-1-(1H-naphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)butyl)morpholine (3ca) white solid; m.p 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), (m, 1H), (m, 1H), (m, 1H), 1.61 (dd, J = 5.2, 10.0 Hz, 1H), (m, 2H), (m, 2H), (m, 4H), 5.53 (bs, 2H), 6.00 (dd, J = 1.6, 6.8 Hz, 2H), (m, 4H); 13 C MR (100 MHz, benzene-d 6 ) δ 22.66, 24.41, 26.92, 38.43, 54.00, 67.59, , , , , , 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: , found: (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 (m, 2H), (m, 3H), (m, 2H), (m, 1H), (m, 6H), (m, 2H), (m, 2H), (m, 4H), 5.56 (bs, 2H), 6.01(dd, J = 2.0, 6.4 Hz, 2H), (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, , , , , , 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: , found: S40

41 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), (m, 2H), (m, 2H), (m, 4H), 5.52 (bs, 2H), 6.04 (dd, J = 1.6, 6.0 Hz, 2H), (m, 4H); 13 C MR (100 MHz, benzene-d 6 ) δ 30.20, 30.42, 41.19, 53.40, 67.70, , , , , , 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: , found: (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 (m, 9H), (m, 2H), (m, 2H), 3.08 (t, J = 6.4 Hz, 2H), (m, 4H), 5.50 (bs, 2H), 6.03 (dd, J = 2.4, 6.0 Hz, 2H), (m, 4H); 13 C MR (100 MHz, benzene-d 6 ) δ 26.57, 27.69, 29.14, 32.56, 45.02, 54.17, (the boron-bound carbon, very weak), 67.49, , , , , , ; 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: , found: (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), (m, 2H), (m, 3H), 2.88 (dd, J = 5.2, 12.8 Hz, 1H), (m, 4H), 5.36 (bs, 2H), 5.91 (dd, J = 2.0, 6.4 Hz, 2H), (m, 9H); 13 C MR (100 MHz, benzene-d 6 ) δ 34.32, 53.45, (the boron-bound carbon, very weak), 67.56, , , , , , , , , , ; 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: , found: (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), (m, 2H), 2.29 (dd, J = 10.8, 12.8 Hz, 1H), (m, 2H), 2.74 (dd, J = 5.2, 12.8 Hz, 1H), (m, 4H), 5.25 (bs, 2H), 5.90 (dd, J = 1.6, 6.4 Hz, 2H), (m, 2H), (m, 2H), (m, 4H); 13 C MR (100 MHz, benzene-d 6 ) δ 33.83, 53.63, (the boron-bound carbon, very weak), 67.49, , (d, J = 21.0 Hz), , , , (d, J = 7.5 Hz), (d, J = 3.0 Hz), , , (d, J = Hz); 11 B MR (128 MHz, S41

42 benzene-d 6 ) δ 30.65; 19 F MR (376 MHz, benzene-d 6 ) δ ; HRMS (APCI) m/z ([M+H] + ) calcd for C 22 H 24 BF 3 O: , found: (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), (m, 2H), 2.26 (m, 3H), 2.70 (dd, J = 5.2, 12.8 Hz, 1H), (m, 4H), 5.19 (bs, 2H), 5.89 (dd, J = 2.0, 6.4 Hz, 2H), 6.84, (d, J = 8.0 Hz, 2H), (m, 4H), 7.22 (d, J = 8.0 Hz, 2H); 13 C MR (100 MHz, benzene-d 6 ) δ 34.66, 53.69, (the boron-bound carbon, very weak), 67.44, , , , (q, J = Hz), (q, J = 3.7 Hz), , (q, J = 32.1 Hz), , , , ; 11 B MR (128 MHz, benzene-d 6 ) δ 31.06; 19 F MR (376 MHz, benzene-d 6 ) δ ; HRMS (APCI) m/z ([M+H] + ) calcd for C 23 H 24 BF 3 3 O: , found: (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), (m, 4H), 3.18 (dd, J = 5.6, 8.4 Hz, 1H), (m, 4H), 5.99 (bs, 2H), 6.14 (dd, J = 2.8, 5.8 Hz, 2H), 6.92 (d, J = 8.0 Hz, 2H), (m, 4H), 7.33 (d, J = 8.0 Hz, 2H); 13 C MR (100 MHz, benzene-d 6 ) δ (the boron-bound carbon, very weak), 50.52, 67.04, 67.39, , , , (q, J = 3.7 Hz), (q, J = Hz), , , (q, J = 32.2 Hz), , , ; 11 B MR (128 MHz, benzene-d 6 ) δ 31.15; 19 F MR (376 MHz, benzene-d 6 ) δ ; HRMS (APCI) m/z ([M+H] + ) calcd for C 23 H 24 BF 3 3 O: , found: (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), (m, 9H), (m, 3H), (m, 5H), (m, 2H), (m, 2H), (m, 2H), 5.67 (bs, 2H), 6.02 (dd, J = 2.0, 6.4 Hz, 2H), (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, (the boron-bound carbon, very weak), , , , , , ; 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 : , found: (1-(2,2,6,6-Tetramethylpiperidin-1-yl)octyl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborini S42

43 ne (3ac) white solid; m.p o C; 1 H MR (400 MHz, benzene-d 6 ) δ 0.94 (t, J = 6.4 Hz, 3H), (m, 13H), (m, 9H), (m, 4H), (m, 3H), (m, 1H), 2.60 (d, J = 10.0 Hz, 1H), 5.71 (bs, 2H), 6.16 (dd, J = 2.0, 6.4 Hz, 2H), (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, , , , , , (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 : , found: (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 (m, 8H), (m, 4H), (m, 2H), (m, 1H), 3.33 (s, 3H), 5.70 (bs, 2H), 6.03 (dd, J = 1.6, 6.8 Hz, 2H), (m, 2H), (m, 6H); 13 C MR (100 MHz, benzene-d 6 ) δ 27.31, 30.27, 31.69, 54.86, 55.38, , , , , , , , , , 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: , found: 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), (m, 10H), (m, 2H), (m, 10H), (m, 2H), (m, 2H), (m, 4H), 5.72 (bs, 2H), 6.08 (dd, J = 2.0, 6.4 Hz, 2H), (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, (the boron-bound carbon, very weak), 53.11, 57.19, 79.21, , , , , , , ; 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 : , found: (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), (m, 1H), (m, 2H), (m, 5H), (m, 2H), (m, 2H), 3.55 (s, 4H), 5.72 (bs, 2H), 6.04 (dd, J = 2.0, 6.0 Hz, 2H), (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, , , , , , 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: , found: S43

44 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), (m, 9H), (m, 1H), (m, 1H), (m, 1H), 1.78 (dd, J = 4.4, 9.2 Hz, 1H), (m, 3H), (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), (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, (the boron-bound carbon, very weak), , , , , , , , , , , , ; 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 : , found: (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), (m, 9H), (m, 1H), (m, 1H), (m, 1H), 1.80 (dd, J = 4.8, 9.2 Hz, 1H), (m, 3H), (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), (m, 4H); 13 C MR (100 MHz, benzene-d 6 ) δ 14.39, 23.10, 26.10, 27.75, (2C), 30.80, 32.36, 50.99, 52.84, (the boron-bound carbon, very weak), , , , , , , , , , ; 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: , found: (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), (m, 2H), (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), (m, 2H), 6.86 (d, J = 5.2 Hz, 1H), (m, 6H); 13 C MR (100 MHz, benzene-d 6 ) δ 26.43, 32.85, 50.16, 52.10, 54.85, , , , , , , , , , , , , , 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: , found: 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 (m, 2H), 0.98 (t, J = 7.2 Hz, 6H), (m, S44

45 5H), (m, 1H), (m, 4H), (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), (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, , , , , , 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 : , found: 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), (m, 3H), (m, 2H), (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), (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, , , , , , , , , , 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 : , found: ,-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), (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, (the boron-bound carbon, very weak), 54.86, 56.22, , , , , , , , , , , , , , ; 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: , found: ,-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), (m, 10H), (m, 1H), (m, 1H), 2.28 (dd, J = 4.0, 10.0 Hz, 1H), (m, 2H), 5.67 (bs, 2H), 6.10 (dd, J = 2.0, 6.4 Hz, 2H), (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, (the boron-bound S45