Rhodium/Lewis Acid Catalyzed Regioselective Addition of 1,3-Dicarbonyl Compounds to Internal Alkynes

Supporting Information for: Rhodium/Lewis Acid Catalyzed Regioselective Addition of 1,3-Dicarbonyl Compounds to Internal Alkynes Wei-Feng Zheng, Qiu-Jing Xu and Qiang Kang* College of Materials Science and Engineering, Fujian Normal University, 8 Shangsan Road, Fuzhou, 350007, China. Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155 Yangqiao Road West, Fuzhou, 350002, China

Table of Contents: 1 General Information S2 2 Optimization conditions S3 3 Synthesis of the substrates S6 4 1 H NMR monitoring experiments S9 5 Mechanistic Experiments S13 6 Control Experiments S15 7 Characterizations S18 8 Copies of 1 H NMR and 13 C NMR spectra of the compounds S43 S1

1. General Information All non-aqueous reactions were performed in oven-dried glassware and standard Schlenk tubes under an atmosphere of nitrogen. 1,2-dichloroethane (DCE), 1,2- dichlorobenzene (ODCB), acetonitrile (CH3CN) were distilled from CaH2 under inert atmosphere. Tetrahydrofuran (THF), dioxane and toluene (PhMe) were distilled from sodium and benzophenone under inert atmosphere. All other solvents and reagents were used as received unless otherwise noted. Thin layer chromatography was performed using silica gel 60 F-254 precoated plates (0.2~0.3 mm) and visualized by short-wave UV (254 nm) irradiation, potassium permanganate, CAM or iodine stain. The 1 H and 13 C NMR spectra were obtained in CDCl3 using a Bruker Avance III spectrometer at 400 and 100 MHz for 1 H and 13 C NMR, respectively. Chemical shifts (δ) for 1 H NMR spectra are recorded in parts per million from tetramethylsilane with the solvent resonance as the internal standard (chloroform, δ 7.26 ppm). Data are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, qn = quintet, m = multiplet and br = broad), coupling constant in Hz, and integration. Chemical shifts for 13 C NMR spectra are recorded in parts per million from tetramethylsilane using the central peak of deuterochloroform (δ 77.00 ppm) as the internal standard. The infrared spectra were recorded on a VERTEX 70 IR spectrometer as KBr pellets, with absorption reported in cm -1. HRMS data were obtained on a Bruker Impact II UHR-TOF system. Melting points were measured on SGW X-4 apparatus. S2

2. Optimization Conditions Table S1: Investigation of the Effect of Solvents. a entry solvent yield of 3a (%) [b] 1 DCE 99 2 Dioxane 14 3 ODCB 43 4 Toluene 18 5 THF 99 6 CH3CN 11 a Reaction conditions: 0.1 mmol 1a, 0.2 mmol 2a, 5 mol% [Rh(COD)Cl]2, 12 mol% DPEphos and 6 mol% Yb(OTf)3 in solvent (0.1 M) at 70 o C, 24 hours. b Determined by GC with n-dodecane as internal standard. Table S2: Optimization of the Temperature. a entry T ( o C) yield of 3a (%) [b] 1 r.t. 6 [c] 2 40 20 [c] 3 60 82 4 70 99 5 80 95 S3

a Reaction conditions: 0.1 mmol 1a, 0.2 mmol 2a, 5 mol% [Rh(COD)Cl]2, 12 mol% DPEphos and 6 mol% Yb(OTf)3 in DCE (0.1 M) at T o C, 24 hours. b Isolated yield. c Incomplete conversion. Table S3: Screening the Loading of Catalyst, Ligand and Lewis Acid. a entry x,y,z (mol %) yield of 3a (%) [b] 1 2,4,2 81 2 3,6,3 88 3 5,5,6 56 4 5,10,6 90 5 5,12,6 99 a Reaction conditions: 0.1 mmol 1a, 0.2 mmol 2a, x mol% [Rh(COD)Cl]2, y mol% DPEphos and z mol% Yb(OTf)3 in DCE (0.1 M) at 70 o C, 24 hours. b Isolated yield. Table S4: Investigation of the Effect of Solvent. a entry solvent yield of 3b (%) [b] 1 DCE 90 2 Dioxane 17 3 ODCB 68 S4

4 Toluene 29 5 THF 72 6 CH3CN 42 a Reaction conditions: 0.1 mmol 1a, 0.1 mmol 2a, 5 mol% [Rh(COD)Cl]2, 12 mol% BINAP and 6 mol% Sc(OTf)3 in solvent (0.1 M) at 70 o C, 48 hours. b Isolated yield. Table S5: Screening the Loading of Catalyst, Ligand and Lewis Acid. a entry x,y,z (mol %) yield of 3b (%) [b] 1 3,6,3 29 2 5,10,5 77 3 5,12,6 90 a Reaction conditions: 0.1 mmol 1a, 0.1 mmol 2a, x mol % [Rh(COD)Cl]2, y mol % BINAP and x mol % Sc(OTf)3 in DCE (0.1 M) at 70 o C, 48 hours. b Isolated yield. S5

3. Synthesis of the Substrates Figure S1: Synthesis of 1,3-dicarbonyl substrates. 1,3-dicarbonyl substrates 1g-1l were prepared according to literature. [1] 1b-1f were commercial reagents. Figure S2: Synthesis of the alkyne substrates. Alkynes 2b, 2c and 2l were prepared according to literature procedure. [2] Alkynes 2g- 2j were prepared from 2k, and 2k were prepared according to literature procedure from 5-hexyn-1-ol. [3] Alkynes 2m [4], 2n [5], 2o [6], and 2p [7] were prepared according to literature procedure. Alkyne 2q was prepared from estrone and 3-pentyn-1-ol. [8] Alkynes 2d was prepared from 4-Ethynylbenzonitrile with 3.0 equiv n-buli and 1.2 S6

equiv CH3I according to literature procedure. [2] 1-Phenylallene 4 was prepared from styrene according to literature procedure. [9] Deuterated 1-Phenyl-1-propyne 2a-d3 was prepared from phenylacetylene according to literature procedure. [10] Alkynes 2a, 2f and 2r were commercial reagents. General Procedure for the Addition of 1,3-Dicarbonyl Compounds to Internal Alkynes General procedure A: In a 10 ml flame dried schlenk tube fitted with a rubber septum and magnetic bar, [Rh(COD)Cl]2 (2.5 mg, 0.005 mmol or 5.0 mg, 0.01 mmol), DPEphos (6.5 mg, 0.012 mmol or 13.0 mg, 0.024 mmol), Yb(OTf)3 (3.8 mg, 0.006 mmol or 7.6 mg, 0.012 mmol) were added in the glove box and then 1,3-dicarbonyl 1 (0.1 mmol or 0.2 mmol), internal alkyne 2 (0.2 mmol or 0.4 mmol) were added by syringe with 1mL or 2 ml anhydrous dichloroethane (DCE). The tube was sealed and heated to 70 o C for 24-48 hours. After the reaction was complete (monitored by TLC), the reaction mixture was directly purified by flash chromatography on silica gel. General procedure B: In a 10 ml flame dried schlenk tube fitted with a rubber septum and magnetic bar, [Rh(COD)Cl]2 (2.5 mg, 0.005 mmol or 5.0 mg, 0.01 mmol), BINAP (7.5 mg, 0.012 mmol or 15.0 mg, 0.024 mmol), Sc(OTf)3 (3.0 mg, 0.006mmol S7

or 6.0 mg, 0.012 mmol) were added in the glove box and then 1,3-dicarbonyl 1 (0.1 mmol or 0.2 mmol), internal alkyne 2 (0.1 mmol or 0.2 mmol) were added by syringe with 1mL or 2 ml anhydrous dichloroethane (DCE). The tube was sealed and heated to 70 o C for 48-72 hours. After the reaction was complete (monitored by TLC), the reaction mixture was directly purified by flash chromatography on silica gel. Procedure for Rhodium/Lewis Acid Catalyzed the Addition of Acetylacetone (1a) to 1-Phenyl-1-Propyne (2a) on Gram Scale. In a 100 ml flame dried schlenk flask fitted with a rubber septum and magnetic bar, [Rh(COD)Cl]2 (123.3 mg, 0.25 mmol), DPEphos (322.8 mg, 0.6 mmol), Yb(OTf)3 (191.4 mg, 0.3 mmol) were added in the glove box and then 1a (0.5 g, 5 mmol), 2a (1.16 g, 10 mmol) were added by syringe with 50 ml anhydrous dichloroethane (DCE). The flask was sealed and heated to 70 o C for 48 hours. After the reaction was complete (monitored by TLC), the solvent was removed under vacuum and the reaction mixture was purified by flash chromatography on silica gel to provide 3a as a colorless oil, 0.99 g, 92% yield (eluting with 2-5% EtOAc in PE (elution gradient)). S8

4. 1 H NMR Monitoring Experiments Figure S3: 1 H NMR monitoring experiment of branched product 3a. S9

Figure S4: Reaction profile of 1 equivalent 1a with 2 equivalent 2a under the reaction condition A. Figure S5: 1 H NMR monitoring experiment of branched product 3a and linear product 4a. S10

Figure S6: Reaction profile of 1 equivalent 1a with 1 equivalent 2a under the reaction condition A. S11

Figure S7: 1 H NMR monitoring experiment of branched product 3a and linear product 4a. Figure S8: Reaction profile of 2 equivelent 1a with 1 equivelent 2a under the reaction condition A. S12

Figure S9: 1 H NMR monitoring experiment of branched product 5k and linear product 6k. Figure S10: Reaction profile of 1k under the reaction condition B. S13

5. Mechanistic Experiments Procedure for the Coupling of Pentane-2,4-dione 1a and 1-Phenylallene 7 The reaction was carried out according to the general procedure A to achieve product 2a as a colorless oil (39.4 mg, 91% yield). Procedure for the Coupling of Pentane-2,4-dione (1a) Deuterated 1-Phenyl-1- propyne (2a-d3) The reaction was carried out according to the general procedure A to achieve product 3a-dn as a pale yellow oil (35.4 mg, 82% yield). S14

7.318 7.300 7.281 7.266 7.232 7.229 7.214 7.208 7.199 7.196 7.179 5.850 5.088 5.061 5.046 5.035 4.274 4.253 4.245 4.196 4.183 4.177 4.167 4.155 4.148 2.248 1.884 9 8 7 6 5 4 3 2 1 0 ppm 2.075 3.118 0.595 0.146 0.910 0.490 3.090 3.000 Figure S11: 1 H NMR of 3a-dn. 6.4 6.2 6.0 5.8 5.6 5.4 5.2 5.0 4.8 4.6 4.4 4.2 4.0 3.8 ppm 0.595 0.146 0.910 0.490 5.850 5.088 5.061 5.046 5.035 4.274 4.253 4.245 4.196 4.183 4.177 4.167 4.155 4.148 Figure S12: 1 H NMR of 3a-dn. S15

6. Control Experiments Figure S13: Crossover experiment. In a 10 ml flame dried schlenk tube fitted with a rubber septum and magnetic bar, [Rh(COD)Cl]2 (8.6 mg, 0.018 mmol), BINAP (26.1 mg, 0.042 mmol), Sc(OTf)3 (10.3 mg, 0.021 mmol) were added in the glove box and then 5f/6f (119.0mg, 0.35 mmol, Branched : Linear = 73:27), pentane-2,4-dione 1a (105 mg, 1.05 mmol, 3 equiv) were added by syringe with 3.5 ml anhydrous dichloroethane (DCE). The tube was sealed and heated to 70 o C for 48 hours. The ratio of 6f and 3a were determined by 1 H NMR analysis of the crude mixture. Figure S14: Investigation of the effect of rhodium catalyst and Lewis acid in retroallylic alkylation. S16

In a 10 ml flame dried schlenk tube fitted with a rubber septum and magnetic bar, [Rh(COD)Cl]2 (4.9 mg, 0.01 mmol), BINAP (14.8 mg, 0.024 mmol), Sc(OTf)3 (5.9 mg, 0.012 mmol) were added in the glove box and then 5f/6f (68 mg, 0.2 mmol, Branched : Linear = 90:10) was added by syringe with 2 ml anhydrous dichloroethane (DCE). The tube was sealed and heated to 70 o C for 24 hours. The ratio of 5f and 6f were determined by 1 H NMR analysis of the crude reaction mixture. Figure S15: Control experiment in the absence of Lewis acid. In a 10 ml flame dried schlenk tube fitted with a rubber septum and magnetic bar, [Rh(COD)Cl]2 (6.4 mg, 0.013 mmol), BINAP (19.3 mg, 0.031 mmol) were added in the glove box and then 5f/6f (88.4 mg, 0.26 mmol, Branched : Linear = 88:12) was added by syringe with 2.6 ml anhydrous dichloroethane (DCE). The tube was sealed and heated to 70 o C for 24 hours. The ratio of 5f/6f was determined by 1 H NMR analysis of crude reaction mixture. S17

Figure S16: Control experiment in the absence of rhodium complex. In a 10 ml flame dried schlenk tube fitted with a rubber septum and magnetic bar, Sc(OTf)3 (5.9 mg, 0.012 mmol) was added in the glove box and then 5f/6f (68 mg, 0.2 mmol, Branched : Linear = 71:29) was added by syringe with 2 ml anhydrous dichloroethane (DCE). The tube was sealed and heated to 70 o C for 24 hours. The ratio of 5f/6f was determined by 1 H NMR analysis of crude reaction mixture. Figure S17: Control experiment in the absence of rhodium complex and Lewis acid. In a 10 ml flame dried schlenk tube fitted with a rubber septum and magnetic bar, 5f/6f (68 mg, 0.2 mmol, Branched : Linear = 71:29) was added followed by 2 ml anhydrous dichloroethane (DCE). The tube was sealed and heated to 70 o C for 24 hours. The ratio of 5f/6f was determined by 1 H NMR analysis of crude reaction mixture. S18

7. Characterizations 1,3-Bis(4-fluorophenyl)propane-1,3-dion Analytical data for 1g: pale yellow solid. 1 H NMR (400 MHz, CDCl3) δ 8.02-7.99 (m, 2H), 7.92 (d, J = 8.6 Hz, 2H), 7.47 (d, J = 8.6 Hz, 2H), 7.17 (t, J = 8.6 Hz, 2H), 6.76 (s, 1H). 1,3-Bis(4-chlorophenyl)propane-1,3-dione Analytical data for 1h: pale yellow solid. 1 H NMR (400 MHz, CDCl3) δ 7.92 (d, J = 8.6 Hz, 4H), 7.47 (d, J = 8.6 Hz, 4H), 6.77 (s, 1H). 1,3-Bis(4-bromophenyl)propane-1,3-dione Analytical data for 1i: pale brown solid. 1 H NMR (400 MHz, CDCl3) δ 7.85 (d, J = 8.6 Hz, 4H), 7.63 (d, J = 8.5 Hz, 4H), 6.77 (s, 1H). 1,3-Di-p-tolylpropane-1,3-dione S19

Analytical data for 1j: pale yellow solid. 1 H NMR (400 MHz, CDCl3) δ 7.89 (d, J = 8.2 Hz, 4H), 7.29 (d, J = 8.1 Hz, 4H), 6.81 (s, 1H), 2.43 (s, 6H). 1,3-Bis(4-methoxyphenyl)propane-1,3-dione Analytical data for 1k: pale yellow solid. 1 H NMR (400 MHz, CDCl3) δ 7.97 (d, J = 8.9 Hz, 1H), 6.97 (d, J = 8.9 Hz, 1H), 6.72 (s, 1H), 3.87 (s, 1H). 1,3-Di(naphthalen-2-yl)propane-1,3-dione Analytical data for 1l: pale yellow solid. 1 H NMR (400 MHz, CDCl3) δ 8.60 (s, 2H), 8.08 (dd, J = 8.6, 1.7 Hz, 2H), 8.02 (d, J = 7.5 Hz, 2H), 7.96 (d, J = 8.6 Hz, 2H), 7.91 (d, J = 7.6 Hz, 2H), 7.60 (dq, J = 6.7, 5.4 Hz, 4H), 7.16 (s, 1H). 1-Methyl-4-(prop-1-yn-1-yl)benzene Analytical data for 2b: colorless oil. 1 H NMR (400 MHz, CDCl3) δ 7.28 (d, J = 8.2 Hz, 2H), 7.08 (d, J = 8.1 Hz, 2H), 2.32 (s, 3H), 2.03 (s, 3H). Ethyl 4-(prop-1-yn-1-yl)benzoate S20

Analytical data for 2c: colorless oil. 1 H NMR (400 MHz, CDCl3) δ 7.97 (d, J = 8.4 Hz, 2H), 7.44 (d, J = 8.4 Hz, 2H), 4.39 (q, J = 7.2 Hz, 2H), 2.08 (s, 3H), 1.40 (t, J = 7.1 Hz, 3H). 1-(4-(Prop-1-yn-1-yl)phenyl)pentan-1-one Analytical data for 2d: yellow oil. 1 H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 8.4 Hz, 2H), 7.46 (d, J = 8.4 Hz, 2H), 2.95 (t, J = 7.4 Hz, 2H), 2.08 (s, 3H), 1.75 (p, J = 7.2 Hz, 2H), 1.45 (dt, J = 15.0, 7.5 Hz, 2H), 0.97 (t, J = 7.2 Hz, 3H). IR (KBr) 1178, 1206, 1508, 1541, 1558, 1602, 1636, 1717, 1734, 2344, 2363, 2958. HRMS (ESI + ) calcd for [C14H16O+Na] + : 223.1093. Found: 223.1093. Pent-3-yn-1-ylbenzene Analytical data for 2e: colorless oil. 1 H NMR (400 MHz, CDCl3) δ 7.31-7.27 (m, 2H), 7.21 (d, 3H), 2.82 (t, J = 7.7 Hz, 2H), 2.44-2.39 (m, 2H), 1.78 (t, J = 2.5 Hz, 3H). ((Hex-4-yn-1-yloxy)methyl)benzene Analytical data for 2g: colorless oil. 1 H NMR (400 MHz, CDCl3) δ 7.34 (d, J = 4.4 Hz, 4H), 7.30-7.25 (m, 1H), 4.51 (s, 2H), 3.56 (t, J = 6.3 Hz, 2H), 2.27-2.22 (m, 2H), 1.81-1.75 (m, 5H). 13 C NMR (100 MHz, CDCl3) δ 138.6, 128.3, 127.6, 127.5, 78.5, 75.7, 72.9, 68.9, 29.1, 15.5, 3.4. IR (KBr) 697, 736, 1027, 1105, 1364, 1454, 2366, 2856, 2919, 3030. HRMS (ESI + ) calcd for [C 13H 16O+Na] + : 211.1093. Found: 211.1093. S21

Hex-4-yn-1-yl benzoate Analytical data for 2h: colorless oil. 1 H NMR (400 MHz, CDCl3) δ 8.05 (dd, J = 7.1 Hz, J = 1.4 Hz, 2H), 7.55 (t, J = 7.4 Hz, 1H), 7.43 (t, J = 7.6 Hz, 2H), 4.41 (t, J = 6.3 Hz, 2H), 2.35-2.30 (m, 2H), 1.95 (p, J = 6.7 Hz, 2H), 1.77 (t, J = 2.5 Hz, 3H). 13 C NMR (100 MHz, CDCl3) δ 166.5, 132.8, 130.3, 129.5, 128.3, 77.7, 76.3, 63.8, 28.1, 15.6, 3.4. IR (KBr) 710, 1026, 1115, 1272, 1450, 1719, 2364, 2919. HRMS (ESI + ) calcd for [C13H14O2+Na] + : 225.0886. Found: 225.0885. tert-butyl(hex-4-yn-1-yloxy)dimethylsilane Analytical data for 2i: colorless oil. 1 H NMR (400 MHz, CDCl3) δ 3.68 (t, J = 6.1 Hz, 2H), 2.22-2.17 (m, 2H), 1.77 (t, J = 2.6 Hz, 3H), 1.67 (p, J = 6.7 Hz, 2H), 0.89 (s, 9H), 0.05 (s, 6H). Hex-4-yn-1-yl 4-methylbenzenesulfonate Analytical data for 2j: colorless oil. 1 H NMR (400 MHz, CDCl3) δ 7.81 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 8.2 Hz, 2H), 4.14 (t, J = 6.5 Hz, 2H), 2.45 (s, 3H), 2.20-2.16 (m, 2H), 1.80 (p, J = 6.8 Hz, 2H), 1.69 (t, J = 2.5 Hz, 3H). Hex-4-yn-1-ol S22

Analytical data for 2k: pale yellow oil. 1 H NMR (400 MHz, CDCl3) δ 3.75 (t, J = 6.1 Hz, 2H), 2.28-2.23 (m, 2H), 1.78 (t, J = 2.6 Hz, 3H), 1.76 (m, J = 6.6 Hz,2H), 1.70 (s, 1H). 6-Chlorohex-2-yne Analytical data for 2l: pale yellow oil. 1 H NMR (400 MHz, CDCl3) δ 3.65 (t, J = 6.4 Hz, 2H), 2.34-2.29 (m, 2H), 1.93 (td, J = 20.2, 13.4, 6.7 Hz, 2H), 1.78 (t, J = 2.5 Hz, 3H). 2,2-Dimethyl-1-phenylhex-4-yn-1-one Analytical data for 2m: colorless oil. 1 H NMR (400 MHz, CDCl3) δ 7.63 (d, J = 7.0 Hz, 2H), 7.46 (t, J = 7.2 Hz, 1H), 7.40 (t, J = 7.6 Hz, 2H), 2.51 (dd, J = 4.9, 2.4 Hz, 2H), 1.77 (t, J = 2.5 Hz, 3H), 1.39 (s, 6H). N-benzyl-N-(but-2-yn-1-yl)-4-methylbenzenesulfonamide Analytical data for 2n: white solid. 1 H NMR (400 MHz, CDCl3) δ 7.81 (d, J = 8.3 Hz, 2H), 7.37-7.29 (m, 7H), 4.32 (s, 2H), 3.88 (q, J = 2.4 Hz, 2H), 2.45 (s, 3H), 1.55 (t, J = 2.4 Hz, 3H). S23

2,2,2-Trifluoro-N-(hex-4-yn-1-yl)acetamide Analytical data for 2o: colorless oil. 1 H NMR (400 MHz, CDCl3) δ 6.89 (s, 1H), 3.51 (q, J = 6.5 Hz, 2H), 2.39-2.24 (m, 2H), 1.80-1.74 (m, 5H). (8R,9S,13S,14S)-13-methyl-3-(pent-3-yn-1-yloxy)-7,8,9,11,12,13,15,16-octahydro- 6H-cyclopenta[a]phenanthren-17(14H)-one Analytical data for 2q: white solid. 1 H NMR (400 MHz, CDCl3) δ 7.20 (d, J = 8.9 Hz, 1H), 6.73 (dd, J = 8.6, 2.7 Hz, 1H), 6.66 (d, J = 2.6 Hz, 1H), 4.04 (t, J = 7.2 Hz, 2H), 2.91 (dd, J = 11.5, 5.0 Hz, 2H), 2.62-2.57 (m, 2H), 2.54 (dd, J = 18.9, 8.7 Hz, 1H), 2.42-2.38 (m, 1H), 2.27-2.22 (m, 1H), 2.19-1.93 (m, 4H), 1.80 (t, J = 2.5 Hz, 3H), 1.66-1.38 (m, 6H), 0.91 (s, 3H). 13 C NMR (100 MHz, CDCl3) δ 220.9, 156.5, 137.7, 132.2, 126.3, 114.6, 112.2, 75.0, 66.5, 50.3, 47.9, 43.9, 38.3, 35.8, 31.5, 29.6, 26.5, 25.8, 21.5, 19.7, 13.8, 3.5, 0.9. IR (KBr) 817, 1007, 1055, 1160, 1254, 1499, 1609, 1738, 2861, 2924. HRMS (ESI + ) calcd for [C23H28O2+H] + : 337.2162. Found: 337.2165. S24

3-(1-Phenylallyl)pentane-2,4-dione (3a) Prepared according to the general procedure A to provide 3a as a colorless oil, 42.8 mg, 99% yield after purification by silica gel column chromatography, eluting with 2-5% EtOAc in PE (elution gradient). The analytical data of 3a was in agreement with those reported [1]. 1 H NMR (400 MHz, CDCl3) δ 7.32-7.27 (m, 2H), 7.23-7.17 (m, 3H), 5.91-5.82 (m, 1H), 5.10-5.05 (m, 2H), 4.26 (d, J = 11.7 Hz, 1H), 4.19 (dd, J = 11.7, 7.7 Hz, 1H), 2.25 (s, 3H), 1.88 (s, 3H). 3-(1-(p-Tolyl)allyl)pentane-2,4-dione (3b) Prepared according to the general procedure A to provide 3b as a yellow oil, 45.5 mg, 99% yield after purification by silica gel column chromatography, eluting with 5-7% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 7.11-7.05 (m, 4H), 5.85 (ddd, J = 17.3, 10.2, 7.7 Hz, 1H), 5.08 (m, 2H), 4.24 (d, J = 11.7 Hz, 1H), 4.13 (dd, J = 11.7, 7.8 Hz, 1H), 2.29 (s, 3H), 2.24 (s, 3H), 1.89 (s, 3H). 13 C NMR (100 MHz, CDCl3) δ 202.9, 202.8, 138.2, 136.8, 136.7, 129.5, 127.7, 116.1, 74.2, 49.4, 29.9, 29.5, 20.9. IR (KBr) 525, 819, 923, 1154, 1356, 1513, 1699, 2364, 2924, 3005. HRMS (ESI + ) calcd for [C15H18O2+Na] + : 253.1199. Found: 253.1201. Ethyl 4-(4-acetyl-5-oxohex-1-en-3-yl)benzoate (3c) S25

Prepared according to the general procedure A to provide 3c as a yellow oil, 57.0 mg, 99% yield after purification by silica gel column chromatography, eluting with 5-7% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 7.99 (d, J = 8.4 Hz, 2H), 7.29 (d, J = 8.3 Hz, 2H), 5.90-5.81 (m, 1H), 5.12 (dd, J = 13.8, 3.3 Hz, 2H), 4.36 (q, J = 7.1 Hz, 2H), 4.32-4.23 (m, 2H), 2.25 (s, 3H), 1.91 (s, 3H), 1.39 (t, J = 7.1 Hz, 3H). 13 C NMR (100 MHz, CDCl3) δ 202.2, 202.0, 166.1, 149.9, 137.1, 130.0, 129.4, 127.9, 117.1, 73.9, 60.8, 49.4, 29.9, 29.4, 14.2. IR (KBr) 768, 857, 927, 1020, 1106, 1182, 1278, 1359, 1609, 1716, 2366, 2982. HRMS (ESI + ) calcd for [C17H20O4+Na] + : 311.1254. Found: 311.1255. 3-(1-(4-Pentanoylphenyl)allyl)pentane-2,4-dione (3d) Prepared according to the general procedure A to provide 3d as a yellow oil, 57.1 mg, 95% yield after purification by silica gel column chromatography, eluting with 5-7% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 7.91 (d, J = 8.4 Hz, 2H), 7.30 (d, J = 8.4 Hz, 2H), 5.89-5.81 (m, 1H), 5.12-5.08 (m, 2H), 4.31-4.23 (m, 2H), 2.94 (t, J = 7.4 Hz, 2H), 2.25 (s, 3H), 1.92 (s, 3H), 1.74 (p, J = 7.6 Hz, 2H), 1.45 (td, J = 15.0, 7.5 Hz, 2H), 0.96 (t, J = 7.4 Hz, 3H). 13 C NMR (100 MHz, CDCl3) δ 202.2, 202.1, 199.9, 145.1, 137.1, 136.0, 128.6, 128.1, 117.3, 73.9, 49.4, 38.23, 30.0, S26

29.4, 26.4, 22.4, 13.8. IR (KBr) 926, 1010, 1183, 1267, 1358, 1605, 1699, 2366, 2958. HRMS (ESI + ) calcd for [C19H24O3+Na] + : 323.1618. Found: 323.1617. 3-(5-Phenylpent-1-en-3-yl)pentane-2,4-dione (3e) Prepared according to the general procedure A to provide 3e as a colorless oil, 30.7 mg, 63% yield after purification by silica gel column chromatography, eluting with 9-12% DCM in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 7.29-7.25 (m, 2H), 7.18 (d, J = 7.2 Hz, 1H), 7.14 (d, J = 7.2 Hz, 2H), 5.60-5.50 (m, 1H), 5.19-5.12 (m, 2H), 3.70 (d, J = 10.4 Hz, 1H), 2.91 (qd, J = 10.4, 3.0 Hz, 1H), 2.73-2.64 (m, 1H), 2.52-2.44 (m, 1H), 2.11 (s, 3H), 2.09 (s, 3H), 1.67-1.58 (m, 1H), 1.53-1.44 (m, 1H). 13 C NMR (100 MHz, CDCl3) δ 203.5, 203.3, 141.5, 137.5, 128.4, 128.3, 125.9, 118.4, 74.6, 43.9, 34.2, 33.0, 29.9, 29.6. IR (KBr) 700, 47, 923, 1149, 1357, 1455, 1698, 2367, 2928. HRMS (ESI + ) calcd for [C16H20O2+Na] + : 267.1356. Found: 267.1357. 3-(Non-1-en-3-yl)pentane-2,4-dione (3f) Prepared according to the general procedure A to provide 3f as a colorless oil, 18.4 mg, 82% yield after purification by silica gel column chromatography, eluting with 33-35% DCM in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 5.51-5.42 (m, 1H), 5.09-5.05 (m, 2H), 3.68 (d, J = 10.6 Hz, 1H), 2.86 (dd, J = 19.4, 9.6 Hz, 1H), 2.20 (s, 3H), 2.10 (s, 3H), 1.28-1.18 (m, 10H), 0.87 (t, J = 6.4 Hz, 3H). 13 C NMR (100 S27

MHz, CDCl3) δ 203.7, 203.6, 137.9, 117.6, 74.8, 44.8, 32.5, 31.6, 30.2, 29.5, 28.9, 26.7, 22.5, 14.0. IR (KBr) 1360, 1457, 1541, 1558, 1699, 2364, 2857, 2928. HRMS (ESI + ) calcd for [C14H24O2+Na] + : 247.1669. Found: 247.1670. 3-(6-(Benzyloxy)hex-1-en-3-yl)pentane-2,4-dione (3g) Prepared according to the general procedure A to provide 3g as a colorless oil, 55.1 mg, 95% yield after purification by silica gel column chromatography, eluting with 5-7% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 7.36-7.26 (m, 5H), 5.51-5.42 (m, 1H), 5.09-5.05 (m, 2H), 4.47 (s, 2H), 3.69 (t, J = 10.6 Hz, 1H), 3.47-3.38 (m, 2H), 2.92 (qd, J = 10.4, 3.4 Hz, 1H), 2.18 (s, 3H), 2.09 (s, 3H), 1.72-1.61 (m, 1H), 1.54-1.48 (m, 1H), 1.43-1.37 (m, 1H), 1.29-1.22 (m, 1H). 13 C NMR (100 MHz, CDCl3) δ 203.5, 203.4, 138.4, 137.6, 128.3, 127.5, 127.5 117.9, 74.6, 72.8, 69.7, 44.1, 30.1, 29.5, 28.9, 26.9. IR (KBr) 698, 739, 923, 1102, 1274, 1358, 1698, 2365, 2858, 2930. HRMS (ESI + ) calcd for [C18H24O3+Na] + : 311.1618. Found: 311.1620. 5-Acetyl-6-oxo-4-vinylheptyl benzoate (3h) Prepared according to the general procedure A to provide 3h as a colorless oil, 54.4 mg, 90% yield after purification by silica gel column chromatography, eluting with 5-7% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 8.03-8.00 (m, 2H), 7.58-7.54 (m, 1H), 7.46 (t, J = 7.6 Hz, 2H), 5.55-5.46 (m, 1H), 5.15-5.11 (m, 2H), S28

4.32-4.24 (m, 2H), 3.72 (t, J = 10.4 Hz, 1H), 2.98 (qd, J = 10.3, 3.1 Hz, 1H), 2.19 (s, 3H), 2.11 (s, 3H), 1.88-1.78 (m, 1H), 1.73-1.62 (m, 1H), 1.54-1.45 (m, 1H), 1.31-1.25 (m, 1H). 13 C NMR (100 MHz, CDCl3) δ 203.3, 203.2, 166.5, 137.3, 132.9, 130.2, 129.5, 128.3, 118.3, 74.5, 64.4, 43.9, 30.1, 29.4, 28.8, 26.1. IR (KBr) 714, 925, 1070, 1116, 1275, 1358, 1452, 1717, 2368, 2929. HRMS (ESI + ) calcd for [C18H22O4+Na] + : 325.1410. Found: 325.1411. 3-(6-((tert-Butyldimethylsilyl)oxy)hex-1-en-3-yl)pentane-2,4-dione (3i) Prepared according to the general procedure A to provide 3i as a colorless oil, 47.4 mg, 76% yield after purification by silica gel column chromatography, eluting with 2-5% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 5.47 (ddd, J = 18.3, 13.5, 9.4 Hz, 1H), 5.07-5.03 (m, 2H), 3.66 (d, J = 10.6 Hz, 1H), 3.55 (t, J = 6.0 Hz, 2H), 2.89 (qd, J = 10.4, 2.7 Hz, 1H), 2.16 (s, 3H), 2.07 (s, 3H), 1.55-1.48 (m, 1H), 1.42-1.32 (m, 2H), 1.23-1.15 (m, 1H), 0.85 (s, 9H), 0.03 (s, 6H). 13 C NMR (100 MHz, CDCl3) δ 203.6, 203.5, 137.8, 117.8, 74.7, 62.6, 44.2, 30.0, 29.9, 29.6, 28.7, 25.9, 18.2, -5.3. IR (KBr) 775, 835, 1099, 1255, 1358, 1472, 1700, 2366, 2857, 2930. HRMS (ESI + ) calcd for [C17H32O3Si+Na] + : 335.2013. Found: 335.2014. 5-Acetyl-6-oxo-4-vinylheptyl 4-methylbenzenesulfonate (3j) S29

Prepared according to the general procedure A to provide 3j as a colorless oil, 56.3 mg, 80% yield after purification by silica gel column chromatography, eluting with 17-20% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 7.77 (d, J = 8.2 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 5.46-5.36 (m, 1H), 5.09-5.02 (m, 2H), 4.00-3.96 (m, 2H), 3.65 (d, J = 10.4 Hz, 1H), 2.84 (qd, J = 10.3, 2.9 Hz, 1H), 2.45 (s, 3H), 2.17 (s, 3H), 2.08 (s, 3H), 1.73-1.67 (m, 1H), 1.57-1.49 (m, 1H), 1.38-1.30 (m, 1H), 1.23-1.16 (m, 1H). 13 C NMR (100 MHz, CDCl3) δ 203.0, 202.9, 144.7, 136.9, 132.9, 129.8, 127.8, 118.5, 74.2, 69.9, 43.6, 30.2, 29.4, 28.1, 26.3, 21.5. IR (KBr) 555, 664, 816, 927, 1176, 1358, 1699, 2366, 2926. HRMS (ESI + ) calcd for [C18H24O5S+Na] + : 375.1237. Found: 375.1237. 3-(6-Hydroxyhex-1-en-3-yl)pentane-2,4-dione (3k) Prepared according to the general procedure A to provide 3k as a colorless oil, 22.6 mg, 57% yield after purification by silica gel column chromatography, eluting with 33-35% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 5.53-5.43 (m, 1H), 5.12-5.08 (m, 2H), 3.70 (d, J = 10.4 Hz, 1H), 3.64 (t, J = 6.0 Hz, 2H), 2.93 (qd, J = 10.3, 2.8 Hz, 1H), 2.21 (s, 3H), 2.11 (s, 3H), 1.72 (s, 1H), 1.65-1.58 (m, 1H), 1.51-1.38 (m, 2H), 1.24-1.18 (m, 1H). 13 C NMR (100 MHz, CDCl3) δ 203.7, 203.4, 137.5, 118.1, 74.6, 62.2, 43.8, 30.3, 29.7, 29.4, 28.6. IR (KBr) 923, 1153, 1359, 1419, 1541, 1697, 2363, 2934. HRMS (ESI + ) calcd for [C11H18O3+Na] + : 221.1154. Found: 221.1149. 3-(6-Chlorohex-1-en-3-yl)pentane-2,4-dione (3l) S30

Prepared according to the general procedure A to provide 3l as a yellow oil, 42.2 mg, 97% yield after purification by silica gel column chromatography, eluting with 5-7% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 5.53-5.42 (m, 1H), 5.13-5.09 (m, 2H), 3.70 (d, J = 10.5 Hz, 1H), 3.56-3.45 (m, 2H), 2. 93 (qd, J = 10.4, 3.1 Hz, 1H), 2.21 (s, 3H), 2.11 (s, 3H), 1.84-1.76 (m, 1H), 1.73-1.66 (m, 1H), 1.52-1.44 (m, 1H), 1.30-1.25 (m, 1H). 13 C NMR (100 MHz, CDCl3) δ 203.3, 203.1, 137.2, 118.3, 74.5, 44.5, 43.6, 30.0, 29.8, 29.5. IR (KBr) 925, 1147, 1358, 1420, 1699, 2367, 2929. HRMS (ESI + ) calcd for [C11H17O2Cl+Na] + : 239.0809. Found: 239.0810. 5-Acetyl-2,2-dimethyl-1-phenyl-4-vinylheptane-1,6-dione (3m) Prepared according to the general procedure A to provide 3m as a colorless oil, 28.3 mg, 47% yield after purification by silica gel column chromatography, eluting with 5-7% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 7.63 (d, J = 7.6 Hz, 2H), 7.49 (t, J = 7.0 Hz, 1H), 7.42 (d, J = 7.4 Hz, 2H), 5.43-5.34 (m, 1H), 5.04-4.94 (m, 2H), 3.71 (d, J = 10.0 Hz, 1H), 3.12 (qd, J = 10.4, 2.7 Hz, 1H), 2.21 (s, 3H), 2.18 (dd, J = 12.0, 3.0 Hz, 1H), 2.08 (s, 3H), 1.53 (dd, J = 13.8, 2.5 Hz, 1H) 1.36 (d, J = 2.7 Hz, 6H). 13 C NMR (100 MHz, CDCl3) δ 208.6, 203.4, 203.2, 138.9, 138.2, 130.8, 128.0, 127.9, 118.2, 74.8, 47.0, 42.6, 42.1, 30.2, 29.9, 28.9, 25.4. IR (KBr) 1361, 1419, 1473, 1558, 1698, 1733, 2365.98, 2971. HRMS (ESI + ) calcd for [C19H24O3+Na] + : 323.1618. Found: 323.1621. S31

N-(3-acetyl-4-oxo-2-vinylpentyl)-N-benzyl-4-methylbenzenesulfonamide (3n) Prepared according to the general procedure A to provide 3n as a colorless oil, 50.4 mg, 61% yield after purification by silica gel column chromatography, eluting with 9-12% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 7.67 (d, J = 8.6 Hz, 2H), 7.33-7.28 (m, 7H), 5.68 (dt, J = 17.2, 9.9 Hz, 1H), 4.95 (dd, J = 10.2, 1.2 Hz, 1H), 4.76 (d, J = 17.2 Hz, 1H), 4.50 (d, J = 14.6 Hz, 1H), 4.10 (d, J = 14.6 Hz, 1H), 3.86 (d, J = 7.0 Hz, 1H), 3.31 (dd, J = 14.2, 7.7 Hz, 1H), 2.94 (dd, J = 14.2, 6.8 Hz, 1H), 2.72 (m, 1H), 2.44 (s, 3H), 2.06 (s, 3H), 1.94 (s, 3H). 13 C NMR (100 MHz, CDCl3) δ 203.9, 203.5, 143.5, 136.2, 136.0, 135.3, 129.7, 128.9, 128.6, 128.1, 127.2, 118.9, 68.6, 54.0, 51.7, 43.3, 30.2, 29.4, 21.4. IR (KBr) 549, 656, 699, 928, 1159, 1339, 1496, 1699, 2364, 2925. HRMS (ESI + ) calcd for [C23H27NO4S+H] + : 414.1734. Found: 414.1731. N-(5-acetyl-6-oxo-4-vinylheptyl)-2,2,2-trifluoroacetamide (3o) Prepared according to the general procedure A to provide 3o as a colorless oil, 45.2 mg, 77% yield after purification by silica gel column chromatography, eluting with 17-20% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 6.72 (s, 1H), 5.52-5.42 (m, 1H), 5.15-5.08 (m, 2H), 3.71 (d, J = 10.8 Hz, 1H), 3.47 (td, J = 13.4, 6.3 Hz, 1H), 3.36 (td, J = 12.4, 5.5 Hz,1H), 2.90 (qd, J = 10.4, 2.9 Hz, 1H), 2.20 (s, S32

3H), 2.11 (s, 3H), 1.68-1.59 (m, 1H), 1.57-1.45 (m, 1H), 1.39-1.32 (m, 1H), 1.26-1.15 (m, 1H). 13 C NMR (100 MHz, CDCl3) δ 203.6, 203.0, 157.2 (q, J = 36.6 Hz), 137.0, 118.6, 115.8 (q, J = 286.3 Hz), 74.1, 43.0, 39.1, 30.5, 29.4, 29.1, 25.8. 19 F NMR (376 MHz, CDCl3) δ -75.93. IR (KBr) 1156, 1361, 1419, 1457, 1508, 1699, 2365, 2940. HRMS (ESI + ) calcd for [C13H18NO3F3+Na] + : 316.1131. Found: 316.1133. 3-(5-(((8R,9S,13S,14S)-13-methyl-17-oxo-7,8,9,11,12,13,14,15,16,17-decahydro- 6H-cyclopenta[a]phenanthren-3-yl)oxy)pent-1-en-3-yl)pentane-2,4-dione (3q) Prepared according to the general procedure A to provide 3q as a yellow oil, 76.1 mg, 87% yield after purification by silica gel column chromatography, eluting with 9-12% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 7.19 (d, J = 8.6 Hz, 1H), 6.69 (dd, J = 8.6, 2.6 Hz, 1H), 6.61 (d, J = 2.5 Hz, 1H), 5.63-5.52 (m, 1H), 5.14-5.10 (m, 2H), 3.97-3.83 (m, 2H), 3.81 (d, J = 10.4 Hz, 1H), 3.22 (qd, J = 10.0, 3.3 Hz, 1H), 2.90-2.87 (m, 2H), 2.53 (dd, J = 18.7, 8.6 Hz, 1H), 2.41-2.37 (m, 1H), 2.23 (s, 3H), 2.20-2.15 (m, 1H), 2.13 (s, 3H), 2.12-1.93 (m, 4H), 1.87-1.79 (m, 1H), 1.69-1.52 (m, 4H), 1.47-1.38 (m, 2H), 1.25 (s, 1H), 0.91 (s, 3H). 13 C NMR (100 MHz, CDCl3) δ 220.9, 203.4, 203.4, 156.6, 137.7, 136.9, 132.1, 126.2, 118.5, 114.4, 112.0, 73.9, 64.7, 50.3, 47.9, 43.9, 41.0, 38.3, 35.8, 31.8, 31.5, 29.8, 29.7, 29.6, 26.5, 25.8, 21.5, 13.8. IR (KBr) 1055, 1159, 1253, 1358, 1499, 1698, 1737, 2366, 2928. HRMS (ESI + ) calcd for [C28H36O4+Na] + : 459.2506. Found: 459.2504. S33

(E)-3-(1-Phenylbut-2-en-1-yl)pentane-2,4-dione (3r) Prepared according to the general procedure A to provide 3r as a colorless oil, 39.6 mg, 43% yield after purification by silica gel column chromatography, eluting with 1-3% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 7.29 (t, J = 7.3 Hz, 2H), 7.19 (t, J = 9.6 Hz, 3H), 5.55-5.44 (m, 2H), 4.23 (d, J = 11.7 Hz, 1H), 4.12(dd, J = 11.6, 7.1 Hz, 1H), 2.23 (s, 3H), 1.87 (s, 3H), 1.61 (d, J = 5.2 Hz, 3H). 13 C NMR (100 MHz, CDCl3) δ 203.0, 202.9, 140.73, 130.7, 128.8, 127.7, 127.4, 126.9, 74.6, 49.1, 30.0, 29.5, 17.8. IR (KBr) 700, 755, 967, 1153, 1356, 1453, 1699, 2363, 2919, 3029. HRMS (ESI + ) calcd for [C15H18O2+Na] + : 253.1199. Found: 253.1200. (E)-3-(4-Phenylbut-3-en-2-yl)pentane-2,4-dione (3r ) Prepared according to the general procedure A to provide 3r as a colorless oil, 41.4 mg, 45% yield after purification by silica gel column chromatography, eluting with 1-3% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 7.33-7.26 (m, 4H), 7.24-7.19 (m, 1H), 6.44 (d, J = 15.9 Hz, 1H), 5.99 (dd, J = 15.9, 8.5 Hz, 1H), 3.70 (d, J = 10.3 Hz, 1H), 3.27-3.15 (m, 1H), 2.22 (s, 3H), 2.13 (s, 3H), 1.08 (d, J = 6.7 Hz, 3H). 13 C NMR (100 MHz, CDCl3) δ 203.5, 203.4, 136.7, 130.9, 130.9, 128.5, 127.5, 126.2, 75.5, 37.8, 29.9, 29.6, 18.8. IR (KBr) 694, 749, 969, 1155, 1357, 1492, 1698, 2362, 2926, 2966, 3026. HRMS (ESI + ) calcd for [C15H18O2+Na] + : 253.1199. Found: 253.1201. S34

4-(1-Phenylallyl)heptane-3,5-dione (5a) Prepared according to the general procedure A to provide 5a as a colorless oil, 24.1 mg, 99% yield after purification by silica gel column chromatography, eluting with 17-20% DCM in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) of 5a: δ 7.28 (d, J = 7.4 Hz, 2H), 7.22-7.16 (m, 3H), 5.86 (ddd, J = 17.1, 10.5, 7.2 Hz, 1H), 5.07-5.03 (m, 2H), 4.27-4.18 (m, 2H), 2.61 (qd, J = 7.5, 1.9 Hz, 2H), 2.26 (dq, J = 18.4, 7.4 Hz, 1H), 2.08 (dq, J = 18.4, 7.2 Hz, 1H), 1.03 (t, J = 7.1 Hz, 3H), 0.72 (t, J = 7.2 Hz, 3H). 1 H NMR (400 MHz, CDCl3) of 6a: δ 7.30 (m, 5H), 6.45 (d, J = 15.6 Hz, 1H), 6.09-6.01 (m, 1H), 3.84 (t, J = 7.0 Hz, 1H), 2.76 (m, 2H), 2.53-2.42 (m, 4H), 1.05 (t, J = 6.8 Hz, 6H). 13 C NMR (100 MHz, CDCl3) of 5a: δ 205.3, 140.1, 138.2, 128.8, 127.9, 127.1, 116.4, 72.9, 49.8, 36.3, 35.6, 7.3, 7.1. IR (KBr) 702, 922, 1101, 1347, 1456, 1699, 1733, 2939, 2979. HRMS (ESI + ) calcd for [C16H20O2+Na] + : 267.1356. Found: 267.1359. 2,6-Dimethyl-4-(1-phenylallyl)heptane-3,5-dione (5b) Prepared according to the general procedure A to provide 5b as a colorless oil, 19.1 mg, 70% yield after purification by silica gel column chromatography, eluting with 17-20% DCM in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) of 5b: δ 7.29 (m, 2H), 7.20 (m, 3H), 5.89 (ddd, J = 17.2, 10.2, 8.2 Hz, 1H), 5.08 (m, 2H), 4.46 (d, J = 11.8 Hz, 1H), 4.29 (dd, J = 11.2, 8.2 Hz, 1H), 2.90-2.83 (m, 1H), 2.51-2.42 (m, 1H), S35

1.09 (dd, J = 15.8, 6.8 Hz, 6H), 0.73 (d, J = 6.8 Hz, 3H), 0.63 (d, J = 6.9 Hz, 3H). 1 H NMR (400 MHz, CDCl3) of 6b: δ 7.29 (m, 5H), 6.45 (d, J = 15.8 Hz, 1H), 6.09 (m, 1H), 4.11 (t, J = 7.0 Hz, 1H), 2.79-2.71 (m, 4H), 1.12 (dd, J = 15.6, 6.8 Hz, 12H). 13 C NMR (100 MHz, CDCl3) of 5b: δ 208.4, 208.3, 140.4, 138.4, 128.7, 128.3, 127.0, 116.7, 71.5, 50.2, 40.6, 40.3, 18.8, 18.2, 18.1, 17.7. IR (KBr) 701, 758, 921, 1058, 1465, 1696, 1728, 2934, 2973. HRMS (ESI + ) calcd for [C18H24O2+Na] + : 295.1669. Found: 295.1667. 4-(6-(Benzyloxy)hex-1-en-3-yl)heptane-3,5-dione (5c) Prepared according to the general procedure A to provide 5c as a colorless oil, 49.6 mg, 77% yield after purification by silica gel column chromatography, eluting with 5-7% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 7.36-7.29 (m, 4H), 7.29-7.25 (m, 1H), 5.49-5.40 (m, 1H), 5.09-5.01 (m, 2H), 4.47 (s, 2H), 3.70 (d, J = 10.9 Hz, 1H), 3.49-3.37 (m, 2H), 2.95 (qd, J = 10.4, 3.1 Hz, 1H), 2.51-2.38 (m, 4H), 1.70-1.61 (m, 1H), 1.54-1.44 (m, 1H), 1.41-1.33 (m, 1H), 1.24-1.19 (m, 1H), 1.01 (t, J = 7.4 Hz, 3H), 0.97 (t, J = 7.4 Hz, 3H). 13 C NMR (100 MHz, CDCl3) δ 206.0, 205.9, 138.4, 137.8, 128.2, 127.5, 127.4, 117.7, 73.1, 72.8, 69.7, 44.3, 36.1, 35.7, 29.0, 26.9, 7.4, 7.2. IR (KBr) 698, 737, 921, 1102, 1352, 1456, 1698, 2857, 2938. HRMS (ESI + ) calcd for [C20H28O3+Na] + : 339.1931. Found: 339.1930. Methyl 2-acetyl-3-phenylpent-4-enoate (5d) S36

Prepared according to the general procedure A to provide 5d as a colorless oil, 21.6 mg, 93% yield after purification by silica gel column chromatography, eluting with 33-35% DCM in PE (elution gradient). Major diastereomer: 1 H NMR (400 MHz, CDCl3): δ 7.31-7.28 (m, 2H), 7.23-7.19 (m, 3H), 6.00-5.86 (m, 1H), 5.12-5.05 (m, 2H), 4.15-4.10 (m, 1H), 4.05-3.98 (m, 1H), 3.73 (s, 3H), 1.98 (s, 3H). 13 C NMR (100 MHz, CDCl3): δ 201.4, 168.4, 139.8, 138.1, 128.8, 127.9, 127.2, 116.3, 64.8, 52.5, 49.5, 29.7. Minor diastereomer: 1 H NMR (400 MHz, CDCl3): δ 7.31-7.28 (m, 2H), 7.23-7.19 (m, 3H), 6.00-5.86 (m, 1H), 5.12-5.05 (m, 2H), 4.15-4.10 (m, 1H), 4.05-3.98 (m, 1H), 3.46 (s, 3H), 2.29 (s, 3H). 13 C NMR (100 MHz, CDCl3): δ 201.6, 168.1, 140.1, 137.8, 128.6, 127.8, 127.1, 116.7, 65.2, 52.3, 49.4, 30.1. IR (KBr) 700, 1157, 1419, 1490, 1541, 1717, 2367, 2953. HRMS (ESI + ) calcd for [C14H16O3+Na] + : 255.0992. Found: 255.0992. 3-Acetyl-3-(1-phenylallyl)dihydrofuran-2(3H)-one (5e) Prepared according to the general procedure A to provide 5e as a colorless oil, 24.2 mg, 98% yield after purification by silica gel column chromatography, eluting with 33-35% DCM in PE (elution gradient). Major diastereomer: 1 H NMR (400 MHz, CDCl3): δ 7.32-7.26 (m, 3H), 7.15 (d, J = 7.6 Hz, 2H), 6.05-5.91 (m, 1H), 5.28-5.19 (m, 1H), 5.02 (dd, J = 16.9, 0.6 Hz, 1H), 4.42 (d, J = 7.0 Hz, 1H), 4.17-4.07 (m, 2H), 3. 07-2.99 (m, 1H), 2.56-2.49 (m, 1H), 2.22 (s, 3H). 13 C NMR (100 MHz, CDCl3): δ 201.1, 174.7, 137.9, 136.1, 128.9, 128.5, 127.6, 119.4, 66.2, 53.0, 26.5, 24.3. Minor diastereomer: 1 H NMR (400 MHz, CDCl3): δ 7.32-7.26 (m, 5H), 6.05-5.91 (m, 1H), 5.28-5.19 (m, 2H), 4.49 (d, J = 8.8 Hz, 1H), 4.00 (q, J = 8.0 Hz, 1H), 3.54 (td, J = 8.6, S37

4.8 Hz, 0.1H), 3.07-2.99 (m, 1H), 2.45 (s, 3H), 2.24-2.16 (m, 1H). 13 C NMR (100 MHz, CDCl3): δ 201.4, 174.4, 137.5, 134.7, 129.1, 128.7, 127.7, 119.0, 66.4, 51.8, 26.2, 25.7. IR (KBr) 703, 931, 1028, 1162, 1375, 1491, 1712, 1760, 2363, 2920. HRMS (ESI + ) calcd for [C15H16O3+Na] + : 267.0997. Found: 267.0992. 2-Cinnamyl-1,3-diphenylpropane-1,3-dione (6f) Prepared according to the general procedure B to provide 6f as a colorless oil, 29.2 mg, 90% yield after purification by silica gel column chromatography, eluting with 2-5% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 7.98 (d, J = 7.8 Hz, 4H), 7.58 (t, J = 7.2 Hz, 2H), 7.47 (t, J = 7.2 Hz, 4H), 7.26 (d, J = 3.6 Hz, 4H), 7.19-7.18 (m, 1H), 6.48 (d, J = 15.8 Hz, 1H), 6.28-6.20 (m, 1H), 5.37 (t, J = 6.6 Hz, 1H), 3.04 (t, J = 6.9 Hz, 2H). 13 C NMR (100 MHz, CDCl3) δ 195.5, 136.9, 135.9, 133.5, 132.5, 128.9, 128.6, 128.4, 127.3, 126.7, 126.1, 57.2, 32.9. IR (KBr) 692, 746, 966, 1263, 1448, 1559, 1696, 2345, 2926, 3026, 3059. HRMS (ESI + ) calcd for [C24H20O2+Na] + : 363.1356. Found: 363.1357. 2-Cinnamyl-1,3-bis(4-fluorophenyl)propane-1,3-dione (6g) Prepared according to the general procedure B to provide 6g as a colorless oil, 23.7 mg, 63% yield after purification by silica gel column chromatography, eluting with 2- S38

5% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 8.00-7.96 (m, 2H), 7.90 (d, J = 8.6 Hz, 2H), 7.44 (d, J = 8.5 Hz, 2H), 7.26 (d, J = 4.2 Hz, 4H), 7.23-7.17 (m, 1H), 7.15 (t, J = 8.5 Hz, 2H), 6.47 (d, J = 15.8 Hz, 1H), 6.24-6.16 (m, 1H), 5.23 (t, J = 6.7 Hz, 1H), 3.01 (t, J = 6.6 Hz, 2H). 13 C NMR (100 MHz, CDCl3) δ 194.2, 193.8, 167.3 (d, J = 255.8 Hz), 140.3, 136.8, 134.2, 132.8, 132.2 (d, J = 2.8 Hz), 131.4 (d, J = 9.4 Hz), 129.9, 129.3, 128.5, 127.5, 126.2, 126.1, 116.3 (d, J = 22.0 Hz), 57.6, 32.9. 19 F NMR (376 MHz, CDCl3) δ -103.63 (tt, J = 8.2, 5.3 Hz). IR (KBr) 741, 847, 965, 1156, 1234, 1399, 1507, 1595, 1697, 2364, 2926. HRMS (ESI + ) calcd for [C24H18O2F2+Na] + : 399.1167. Found: 399.1161. 1,3-Bis(4-chlorophenyl)-2-cinnamylpropane-1,3-dione (6h) Prepared according to the general procedure B to provide 6h as a colorless oil, 30.7 mg, 75% yield after purification by silica gel column chromatography, eluting with 2-5% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 7.89 (d, J = 8.6 Hz, 4H), 7.42 (d, J = 8.6 Hz, 4H), 7.26-7.25 (m, 4H), 7.23-7.17 (m, 1H), 6.46 (d, J = 15.8 Hz, 1H), 6.23-6.16 (m, 1H), 5.21 (t, J = 6.4 Hz, 1H), 3.00 (t, J = 6.7 Hz, 2H). 13 C NMR (100 MHz, CDCl3) δ 194.2, 140.3, 136.7, 134.2, 132.8, 129.9, 129.3, 128.5, 127.5, 126.1, 126.1, 57.5, 32.9. IR (KBr) 741, 1093, 1263, 1399, 1588, 1697, 2362, 3026. HRMS (ESI + ) calcd for [C24H18O2Cl2+Na] + : 431.0576. Found: 431.0573. 1,3-Bis(4-bromophenyl)-2-cinnamylpropane-1,3-dione (6i) S39

Prepared according to the general procedure B to provide 6i as a colorless oil, 32.9 mg, 66% yield after purification by silica gel column chromatography, eluting with 2-5% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 7.80 (d, J = 8.6 Hz, 4H), 7.60 (d, J = 8.6 Hz, 4H), 7.28-7.25 (m, 4H), 7.22-7.17 (m, 1H), 6.46 (d, J = 15.6 Hz, 1H), 6.23-6.15 (m, 1H), 5.21 (t, J = 6.7 Hz, 1H), 3.00 (t, J = 6.6 Hz, 2H). 13 C NMR (100 MHz, CDCl3) δ 194.4, 136.7, 134.6, 132.9, 132.3, 130.0, 129.1, 128.5, 127.5, 126.2, 126.0, 57.5, 32.8. IR (KBr) 737, 840, 1008, 1071, 1262, 1396, 1583, 1697, 2363, 3026. HRMS (ESI + ) calcd for [C24H18O2Br2+Na] + : 518.9566. Found: 518.9564. 2-Cinnamyl-1,3-di-p-tolylpropane-1,3-dione (6j) Prepared according to the general procedure B to provide 6j as a colorless oil, 27.9 mg, 76% yield after purification by silica gel column chromatography, eluting with 2-5% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 8.2 Hz, 4H), 7.26-7.22 (m, 8H), 7.19-7.16 (m, 1H), 6.47 (d, J = 15.8 Hz, 1H), 6.28-6.20 (m, 1H), 5.30 (t, J = 6.8 Hz, 1H), 3.00 (t, J = 6.8 Hz, 2H), 2.38 (s, 6H). 13 C NMR (100 MHz, CDCl3) δ 195.2, 144.4, 137.1, 133.5, 132.2, 129.6, 128.7, 128.4, 127.2, 127.0, 126.1, 57.2, 33.0, 21.6. IR (KBr) 741, 818, 964, 1179, 1265, 1559, 1691, 2365, 2920, 3028. HRMS (ESI + ) calcd for [C26H24O2+Na] + : 391.1669. Found: 391.1670. S40

2-Cinnamyl-1,3-bis(4-methoxyphenyl)propane-1,3-dione (6k) Prepared according to the general procedure B to provide 6k as a colorless oil, 36.0 mg, 90% yield after purification by silica gel column chromatography, eluting with 9-12% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 7.97 (d, J = 8.9 Hz, 4H), 7.27-7.22 (m, 4H), 7.19-7.16 (m, 1H), 6.91 (d, J = 8.9 Hz, 4H), 6.47 (d, J = 15.8 Hz, 1H), 6.28-6.20 (m, 1H), 5.23 (t, J = 6.5 Hz, 1H), 3.83 (s, 6H), 3.00 (t, J = 6.8 Hz, 2H). 13 C NMR (100 MHz, CDCl3) δ 194.1, 163.8, 137.1, 132.2, 130.9, 129.0, 128.4, 127.2, 127.1, 126.1, 114.0, 57.2, 55.5, 33.1. IR (KBr) 745, 842, 1027, 1168, 1261, 1599, 1685, 2365, 2839, 2935. HRMS (ESI + ) calcd for [C26H24O4+Na] + : 423.1567. Found: 423.1568. 2-Cinnamyl-1,3-di(naphthalen-2-yl)propane-1,3-dione (6l) Prepared according to the general procedure B to provide 6l as a colorless oil, 35.3 mg, 80% yield after purification by silica gel column chromatography, eluting with 5-7% EtOAc in PE (elution gradient). 1 H NMR (400 MHz, CDCl3) δ 8.55 (s, 2H), 8.06 (dd, J = 8.6, 1.4 Hz, 2H), 7.88-7.80 (m, 6H), 7.60 (t, J = 7.6 Hz, 2H), 7.52 (t, J = 7.6 Hz, 2H), 7.24 (dt, J = 14.8, 6.7 Hz, 4H), 7.18-7.14 (m, 1H), 6.54 (d, J = 15.8 Hz, 1H), 6.38-6.30 (m, 1H), 5.66 (t, J = 6.7 Hz, 1H), 3.18 (t, J = 6.8 Hz, 2H). 13 C NMR (100 MHz, CDCl3) δ 195.5, 136.9, 135.7, 133.4, 132.5, 132.4, 130.5, 129.7, 128.9, 128.8, S41

128.4, 127.7, 127.3, 126.9, 126.8, 126.1, 124.1, 57.7, 33.2. IR (KBr) 745, 820, 1123, 1176, 1278, 1466, 1689, 2366, 3057. HRMS (ESI + ) calcd for [C32H24O2+Na] + : 463.1669. Found: 463.1665. References: [1] T. M. Beck, B. Breit, Org. Lett. 2016, 18, 124-127. [2] T. Fujihara, Y. Tani, K. Semba, J. Terao, Y. Tsuji, Angew. Chem. Int. Ed. 2012, 51, 11487-11490. [3] F. A. Cruz, Z. Chen, S. I. Kurtoic, V. M. Dong, Chem. Commun. 2016, 52, 5836-5839. [4] H. Kusama, K. Ishida, H. Funami, N. Iwasawa, Angew. Chem. Int. Ed. 2008, 47, 4903-4905. [5] S. Arai, T. Sato, A. Nishida, Adv. Synth. Catal. 2009, 351, 1897-1904. [6] J. M. Carney, P. J. Donoghue, W. M. Wuest, O. Wiest, P. Helquist, Org. Lett. 2008, 10, 3903-3906. [7] S. Holing, B. Haberlag, M. Tamm, J. Collatz, P. Mack, J. L. M. Steidle, M. Vences, S. Schulz, Chem. Eur. J. 2014, 20, 3183-3191. [8] Z. Xu, H. Chen, Z. Wang, A. Ying, L. Zhang, J. Am. Chem. Soc. 2016, 138, 5515-5518. [9] T. Kippo, T. Fukuyama, I. Ryu, Org. Lett. 2011, 13, 3864-3867. [10] T. Jiang, X. Quan, C. Zhu, P. G. Andersson, J.-E. Beckvall, Angew. Chem. Int. Ed. 2016, 55, 5824-5826. S42

8. Copies of 1 H NMR and 13 C NMR Spectra of the Compounds 9 8 7 6 5 4 3 2 1 0 ppm 2.038 2.027 2.000 2.009 1.029 8.024 8.018 8.010 8.006 8.001 7.993 7.988 7.930 7.925 7.908 7.478 7.457 7.196 7.191 7.175 7.153 6.758 Figure S18: 1 H NMR of 1g 9 8 7 6 5 4 3 2 1 0 ppm 4.049 4.000 1.015 7.932 7.911 7.480 7.458 6.768 Figure S19: 1 H NMR of 1h S43

9 8 7 6 5 4 3 2 1 0 ppm 4.149 4.075 1.052 7.857 7.835 7.645 7.623 6.769 Figure S20: 1 H NMR of 1i 9 8 7 6 5 4 3 2 1 0 ppm 4.079 4.103 1.000 6.050 7.897 7.876 7.297 7.277 6.809 2.431 Figure S21: 1 H NMR of 1j S44

9 8 7 6 5 4 3 2 1 0 ppm 4.000 4.034 1.010 6.032 7.971 7.966 7.954 7.949 6.988 6.983 6.971 6.965 6.732 3.885 Figure S22: 1 H NMR of 1k 9 8 7 6 5 4 3 2 1 0 ppm 2.000 2.028 2.002 2.083 2.094 4.084 1.005 8.090 8.072 8.068 8.030 8.011 7.973 7.952 7.921 7.902 7.633 7.629 7.615 7.612 7.598 7.593 7.579 7.576 7.562 7.164 Figure S23: 1 H NMR of 1l S45

9 8 7 6 5 4 3 2 1 0 ppm 2.000 2.037 3.039 3.035 7.286 7.266 7.087 7.067 2.322 2.032 Figure S24: 1 H NMR of 2b 9 8 7 6 5 4 3 2 1 0 ppm 2.013 2.000 2.136 3.061 3.040 7.967 7.946 7.442 7.422 4.393 4.375 4.357 4.339 2.075 1.404 1.386 1.369 Figure S25: 1 H NMR of 2c S46

9 8 7 6 5 4 3 2 1 0 ppm Figure S26: 1 H NMR of 2d 199.838 135.659 131.565 128.784 127.908 89.534 79.277 77.317 76.999 76.681 38.290 26.430 22.442 13.901 4.447 2.000 2.007 2.005 3.012 2.039 2.082 3.009 7.883 7.879 7.867 7.862 7.459 7.455 7.443 7.438 2.953 2.935 2.916 2.078 1.745 1.726 1.721 1.708 1.689 1.670 1.448 1.430 1.411 1.396 1.392 1.378 1.374 1.355 0.966 0.948 0.930 200 180 160 140 120 100 80 60 40 20 ppm Figure S27: 13 C NMR of 2d S47

9 8 7 6 5 4 3 2 1 0 ppm 2.135 3.108 2.047 2.000 3.251 7.307 7.286 7.277 7.270 7.219 7.201 2.817 2.797 2.778 2.443 2.437 2.431 2.424 2.417 2.411 2.405 2.398 2.392 2.386 1.781 1.774 1.768 Figure S28: 1 H NMR of 2e 9 8 7 6 5 4 3 2 1 0 ppm 4.024 1.019 2.066 2.056 2.000 4.967 7.343 7.332 7.301 7.291 7.281 7.270 7.258 7.251 4.511 3.571 3.556 3.540 2.275 2.269 2.262 2.257 2.251 2.245 2.239 2.233 2.227 2.221 1.812 1.796 1.779 1.767 1.761 1.754 1.746 Figure S29: 1 H NMR of 2g S48

138.567 128.315 127.579 127.470 78.531 77.319 77.001 76.684 75.702 72.883 68.971 29.147 15.555 3.430 200 180 160 140 120 100 80 60 40 20 ppm Figure S30: 13 C NMR of 2g 9 8 7 6 5 4 3 2 1 0 ppm 2.000 1.012 2.034 2.072 2.073 2.100 3.053 8.054 8.037 8.033 7.571 7.568 7.553 7.537 7.534 7.531 7.454 7.434 7.415 4.430 4.415 4.399 2.352 2.345 2.339 2.334 2.328 2.321 2.316 2.311 2.304 2.298 1.980 1.963 1.946 1.930 1.913 1.773 1.767 1.760 Figure S31: 1 H NMR of 2h S49

166.543 132.838 130.343 129.541 128.298 77.708 77.316 76.999 76.681 76.333 63.788 28.170 15.630 3.401 200 180 160 140 120 100 80 60 40 20 ppm Figure S32: 13 C NMR of 2h 9 8 7 6 5 4 3 2 1 0 ppm 2.065 2.047 3.000 2.048 9.024 6.033 3.695 3.680 3.665 2.227 2.220 2.214 2.208 2.203 2.196 2.190 2.185 2.178 2.172 1.778 1.772 1.766 1.707 1.691 1.674 1.658 1.641 0.895 0.054 Figure S33: 1 H NMR of 2i S50

9 8 7 6 5 4 3 2 1 0 ppm 2.095 2.095 2.091 3.133 2.013 2.030 3.000 7.812 7.791 7.359 7.338 4.152 4.136 4.121 2.451 2.209 2.203 2.196 2.191 2.185 2.179 2.173 2.168 2.162 2.156 1.829 1.813 1.796 1.780 1.764 1.694 1.688 1.682 Figure S34: 1 H NMR of 2j 9 8 7 6 5 4 3 2 1 0 ppm 2.000 2.003 3.078 2.044 1.036 3.768 3.752 3.737 2.284 2.278 2.271 2.267 2.261 2.254 2.248 2.243 2.237 2.231 1.786 1.779 1.773 1.766 1.750 1.733 1.717 1.700 Figure S35: 1 H NMR of 2k S51

9 8 7 6 5 4 3 2 1 0 ppm 2.000 2.012 2.462 3.258 3.666 3.650 3.634 2.338 2.332 2.328 2.321 2.315 2.311 2.305 2.298 1.955 1.939 1.922 1.906 1.785 1.779 1.772 Figure S36: 1 H NMR of 2l 9 8 7 6 5 4 3 2 1 0 ppm 2.000 1.044 2.020 2.019 3.003 6.057 7.648 7.630 7.627 7.478 7.467 7.460 7.454 7.444 7.441 7.417 7.398 7.381 7.262 2.522 2.516 2.510 2.504 1.774 1.767 1.761 1.395 Figure S37: 1 H NMR of 2m S52

9 8 7 6 5 4 3 2 1 0 ppm 2.000 7.044 2.028 2.033 3.068 3.047 7.811 7.790 7.368 7.363 7.346 7.345 7.335 7.330 7.324 7.316 7.310 7.303 7.296 7.286 4.319 3.884 3.879 3.873 3.867 2.445 1.546 1.540 1.534 Figure S38: 1 H NMR of 2n 9 8 7 6 5 4 3 2 1 0 ppm 0.913 2.000 2.016 5.008 6.890 3.531 3.516 3.500 3.484 2.290 2.284 2.277 2.268 2.261 2.255 2.252 2.245 2.239 1.787 1.781 1.774 Figure S39: 1 H NMR of 2o S53

9 8 7 6 5 4 3 2 1 0 ppm Figure S40: 1 H NMR of 2q 220.870 156.473 137.704 132.214 126.278 114.590 112.162 77.316 76.998 76.680 75.049 66.465 50.319 47.934 43.898 38.278 35.801 31.503 29.574 26.468 25.848 21.518 19.741 13.779 3.471 1.006 1.000 1.002 2.023 2.005 1.961 1.032 1.037 1.035 4.088 2.919 6.471 3.027 7.259 7.205 7.183 6.734 6.728 6.713 6.706 6.659 6.652 4.040 4.022 4.004 2.898 2.882 2.872 2.620 2.614 2.608 2.602 2.596 2.590 2.584 2.578 2.489 2.469 2.380 2.165 2.142 2.021 1.966 1.961 1.944 1.803 1.796 1.790 1.623 1.600 1.593 1.572 1.545 1.532 1.502 1.482 1.477 0.907 220 200 180 160 140 120 100 80 60 40 20 ppm Figure S41: 13 C NMR of 2q S54

9 8 7 6 5 4 3 2 1 0 ppm 2.245 3.010 1.000 2.046 1.011 1.002 3.084 3.073 7.317 7.299 7.279 7.268 7.231 7.213 7.207 7.196 7.178 5.909 5.890 5.884 5.865 5.847 5.841 5.822 5.099 5.074 5.056 5.054 5.048 4.276 4.247 4.195 4.176 4.166 4.147 2.248 1.884 Figure S42: 1 H NMR of 3a S55

9 8 7 6 5 4 3 2 1 0 ppm Figure S43: 1 H NMR of 3b 202.950 202.826 138.202 136.775 136.738 129.549 127.699 116.178 77.317 76.999 76.681 74.252 49.383 29.964 29.512 20.941 4.017 1.000 2.041 1.029 1.012 3.052 3.028 3.036 7.114 7.093 7.077 7.061 7.057 5.890 5.870 5.864 5.846 5.845 5.827 5.821 5.802 5.080 5.049 5.037 5.024 4.251 4.222 4.156 4.136 4.127 4.107 2.294 2.239 1.891 200 180 160 140 120 100 80 60 40 20 ppm Figure S44: 13 C NMR of 3b S56

9 8 7 6 5 4 3 2 1 0 ppm Figure S45: 1 H NMR of 3c 202.173 202.046 166.077 144.998 137.133 130.065 129.397 127.884 117.176 77.316 76.998 76.680 73.888 60.879 49.419 29.973 29.388 14.208 2.006 2.003 1.000 2.041 2.170 2.038 3.022 3.052 3.113 7.998 7.977 7.291 7.270 5.899 5.881 5.874 5.863 5.856 5.838 5.831 5.830 5.813 5.120 5.112 5.086 5.077 4.388 4.370 4.352 4.335 4.306 4.277 4.254 4.242 4.225 2.253 1.907 1.396 1.378 1.361 200 180 160 140 120 100 80 60 40 20 ppm Figure S46: 13 C NMR of 3c S57

9 8 7 6 5 4 3 2 1 0 ppm Figure S47: 1 H NMR of 3d 202.201 202.105 199.903 145.100 137.111 136.017 128.675 128.119 117.292 77.319 77.001 76.683 73.934 49.431 38.228 30.007 29.451 26.362 22.408 13.862 2.055 2.195 1.000 2.066 2.081 2.111 3.043 3.100 2.202 2.339 3.202 7.913 7.893 7.305 7.284 5.893 5.875 5.868 5.850 5.832 5.825 5.823 5.808 5.807 5.125 5.116 5.090 5.084 5.082 4.306 4.278 4.255 4.243 4.226 2.946 2.928 2.909 2.254 1.918 1.741 1.722 1.704 1.685 1.666 1.446 1.428 1.409 1.390 1.372 1.353 0.964 200 180 160 140 120 100 80 60 40 20 ppm Figure S48: 13 C NMR of 3d S58

9 8 7 6 5 4 3 2 1 0 ppm Figure S49: 1 H NMR of 3e 203.502 203.359 141.470 137.518 128.396 128.359 125.948 118.415 77.317 77.000 76.682 74.583 43.927 34.237 33.023 29.906 29.586 2.393 1.068 2.083 1.038 2.071 1.000 1.042 1.093 1.079 3.037 2.871 1.350 1.007 7.289 7.285 7.271 7.260 7.252 7.197 7.179 7.137 7.119 5.594 5.570 5.552 5.545 5.528 5.503 5.188 5.185 5.162 5.119 3.703 3.677 2.921 2.914 2.897 2.890 2.685 2.674 2.661 2.648 2.521 2.503 2.496 2.486 2.478 2.112 2.089 1.645 1.637 1.629 1.620 1.612 1.605 1.505 1.493 1.471 200 180 160 140 120 100 80 60 40 20 ppm Figure S50: 13 C NMR of 3e S59

9 8 7 6 5 4 3 2 1 0 ppm Figure S51: 1 H NMR of 3f 203.718 203.617 137.928 117.591 77.317 77.000 76.682 74.759 44.458 32.506 31.661 30.164 29.495 28.962 26.708 22.542 14.014 1.065 2.032 1.000 1.003 3.014 3.003 10.091 3.030 5.512 5.488 5.482 5.473 5.466 5.458 5.450 5.444 5.420 5.088 5.060 5.049 3.683 3.656 2.897 2.872 2.848 2.824 2.196 2.101 1.294 1.279 1.269 1.258 1.242 1.195 1.182 0.885 0.869 0.851 200 180 160 140 120 100 80 60 40 20 ppm Figure S52: 13 C NMR of 3f S60