Construction of Vicinal Quaternary Carbon Centers via Cobalt- Catalyzed Asymmetric Reverse Prenylation

Transcription

1 Supporting Information Construction of Vicinal Quaternary Carbon Centers via Cobalt- Catalyzed Asymmetric Reverse Prenylation Minghe Sun, Jia-Feng Chen, Shufeng Chen, Changkun Li* Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering Shanghai Jiao Tong University. 800 Dongchuan Road, Shanghai , People s Republic of China Inner Mongolia Key Laboratory of Fine Organic Synthesis, Department of Chemistry and Chemical Engineering. Inner Mongolia University. Hohhot , People s Republic of China 1. General Information 1 2. Substrate Compounds Product Compounds Procedure for the Synthesis of 3a-3t and Co(dppbz)2Cl Optimization of Reaction Conditions.5 6. Spectra Data for New Compounds.6 7. X-Ray Data for Compound 3k, 3s and Co(dppbz)2Cl NMR Spectra HPLC Results References..64

2 1 1. General Information Air and moisture sensitive reactions were carried out in oven-dried glassware sealed with rubber septa under dry argon atmosphere. All reagents were purchased from commercial suppliers without further purification. Solvent purification was conducted by solvent purification system (Vigor YJC-7). Column chromatography was performed using mesh silica gels. The NMR spectra were recorded on a Bruker-500 instrument (500 MHz, 1 H; 126 MHz, 13 C), spectrometer with chemical shifts reported in ppm relative to the residual deuterated solvent and the internal standard tetramethylsilane. Data for 1 H NMR are recorded as follows: chemical shift (δ, ppm), multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet or unresolved, br = broad singlet, coupling constant(s) in Hz, integration). High-resolution mass spectra (HRMS) were performed at Instrumental Analysis Center of Shanghai Jiao Tong University with electrospray spectrometer Waters Micromass Q-TOF Premier Mass Spectrometer. The single crystal X-ray diffraction analysis was measured at Instrumental Analysis Center of Shanghai Jiao Tong University with D8 Venture. The ee values were determined by HPLC using a Daicel chiral column. Melting points were measured with Hanon MP100 melting point apparatus. Optical rotations were measured on an Anton Paar MCP100 automatic polarimeter using a 100 mm path-length cell at 589 nm.

3 2 2. Substrate Compounds Compound 1a [1], 1b [2], 1c [2], 1d [3], 1e [2], 1f [2], 1g [2], 1h [2 ], 1i [2], 1j [2], 1m [2], 1n [2], 1o [2] were prepared [1], [2], [3] following a reported procedure.

4 Compound 2a [4], 2b [6], 2c [6], 2d [4], 2f [4], 2g [5] were prepared following a reported procedure. [4], [5], [6] Compound 2e were purchased from Alfa Aesar. 3

5 3. Product Compounds 4

6 5 4. General Procedure for the Synthesis of 3a-3t and Co(dppbz)2Cl The Synthesis of 3a-3t : In a glove box, Co(BF 4) 2 (0.01 mmol, 0.05 eq), (S,S)-Ph-BPE (0.01 mmol, 0.05 eq) and zinc (0.01 mmol, 0.05 eq) were added to a dry reaction tube equipped with a magnetic stir bar. Then CH 3CN (1 ml) was added and the mixture was stirred at room temperature for 30 min. Allyl carbonate (0.30 mmol, 1.5 eq) and β-ketoester (0.2 mmol, 1.0 eq) were added to the mixture. The reaction was warmed to 40 o C and stirred for hours. The reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. The residue was purified by flash column chromatography to give the desired product. The Synthesis of Co(dppbz) 2Cl : CoCl 2 ( mg, 1.0 mmol) is added to a round bottom flask under N 2 atmosphere. EtOH (15 ml) is added, followed by solid dppbz ( mg, 1.0 mmol). The solution turns blue, and the mixture is heated to 70 o C for 1 hour. NaBH 4 (34.00 mg, 0.9 mmol) is added against a flow of N 2 and the reaction is cooled to room temperature. The mixture exotherms slightly and begins to turn green. Stirring is continued until the observed effervescence ceases. Once the reaction mixture has returned to room temperature, n-hexane is added to seperate out the precipitate. The precipitate is collected on a Büchner funnel and washed with n-hexane. The solid is dried in vacuo to yield Co(dppbz) 2Cl as a black solid ( mg, 0.43 mmol, 86%). 5.Optimization of reaction conditions

7 6 6. Spectra Data for New Compounds tert-butyl 1-oxo-6-phenyl-1,2,3,4-tetrahydronaphthalene-2-carboxylate. 6-Phenyl-3,4- dihydronaphthalen-1(2h)-one (1.1 g, 5.0 mmol, 1.0 equiv) in dry THF (5 ml) was added to a suspension of NaH (0.4 g, 10.0 mmol, 2.0 equiv, 60% dispersion in mineral oil) in dry THF (25 ml) at room temperature. The solution was heated to reflux and tert-butyl 1H-pyrrole-1-carboxylate (1.7 g, 10.0 mmol, 2.0 equiv) in dry THF (3 ml) was added dropwise. The solution was stirred at reflux until completion as indicated by TLC. After cooling to 0 o C, the solution was acidified with 1 N HCl. The two layers were seperated and the aquous layer was extracted with EtOAc (10 ml* 3). The combined organic layer was washed with brine (30 ml), dried by Na 2SO 4) and concentrated under reduced pressure. The residue was purified by flash silica gel chromatography to get a yellow oil (1.0 g, 62% yield). R f = 0.40 (20:1 PE/EA). 1 H NMR (500 MHz, CDCl 3): δ (s, 0.53 H), 8.14 (d, J = 8.2 Hz, 0.4 H), 7.88 (d, J = 8.0 Hz, 0.6 H), (m, 2.0 H), (m, 5.0 H), 3.56 (dd, J = 9.8, 4.7 Hz, 0.4 H), (m, 0.8 H), (m, 1.2 H), 2.59 (dd, J = 8.7, 6.9 Hz, 1.2 H), 2.53 (dtd, J = 13.8, 9.3, 4.6 Hz, 0.4 H), 2.40 (ddt, J = 13.5, 6.4, 4.7 Hz, 0.4 H), 1.59 (s, 5.4 H), 1.53 (s, 3.6 H); 13 C NMR (126 MHz, CDCl 3) δ , , , , , , , , , , , , , , , , , , , , , , , , 98.37, 81.83, 81.29, 55.39, 28.37, 28.06, 27.78, 26.57, HRMS (ESI): C 21H 22O 3 [M+Na] + calcd: , found: tert-butyl 1-oxo-6-(phenylethynyl)-1,2,3,4-tetrahydronaphthalene-2-carboxylate. Compound 1l was synthesized following the procedure above from 6-(phenylethynyl)-3,4-dihydronaphthalen-1(2H)- one (1.23 g, 5.0 mmol) to get a yellow oil (1.3 g, 76% yield). R f = 0.26 (20:1 PE/EA). 1 H NMR (500 MHz, CDCl 3): δ (s, 1 H), (m, 0.5 H), 7.79 (d, J = 8.0 Hz, 1 H), (m, 3 H), (m, 2 H), (m, 6 H), 3.53 (dd, J = 9.6, 4.7 Hz, 0.5 H), (m, 1 H), 2.83 (dd, J = 16.7, 9.3 Hz, 2 H), 2.56 (dd, J = 8.8, 6.8 Hz, 2 H), 2.49 (dtd, J = 13.8, 9.2, 4.6 Hz, 0.5 H), 2.36 (ddt, J = 13.5, 6.5, 4.7 Hz, 0.5 H), 1.58 (s, 9 H), 1.51 (s, 4.5 H); 13 C NMR (126 MHz, CDCl 3): δ , , , , , , , , , , , , , , , , , , , , , , , , , 99.08, 92.87, 91.01, 89.41, 88.71, 81.92, 81.46, 55.25, 28.34, 28.03, 28.01, 27.92, 27.63, 27.32, 26.34, HRMS (ESI): C 23H 22O 3 [M+Na] + calcd: , found: Methyl (1-vinylcyclobutyl) carbonate. A flame-dried round-bottomed flask equipped with a magnetic stir bar was charged with THF (30.0 ml) and 1-vinylcyclobutan-1-ol (1.0 g, 10.2 mmol) under nitrogen

8 7 atmosphere. The solution was cooled to 78 C, and n-butyl lithium (13.26 mmol, 8.3 ml of a 1.6 M solution) was added dropwise over a period of 30 minutes. Then the solution was stirred at 78 C for 30 min. Methyl chloroformate (2.4 ml, 30.6 mmol) was added dropwise at 78 C, and the solution was warmed to 0 C for 2 hours followed by gradually warming to room temperature overnight. The reaction was re-cooled to 0 C and quenched with 100 ml of a 3:2 mixture of diethyl ether and ice water, poured into a separatory funnel and extracted into diethyl ether (3 x 100 ml). The combined organic layer was dried over magnesium sulfate, filtered, and concentrated in vacuo. The crude reaction mixture was purified on silica gel (50:1 PE:EA) to afford a clear, colorless oil (0.82 g, 52% yield). Rf = 0.35 (20:1 PE:EA, stain in KMnO4). 1 H NMR (500 MHz, CDCl 3): δ 6.15 (dd, J = 17.4, 10.8 Hz, 1 H), (m, 2 H), 3.75 (s, 3 H), (m, 4 H), (m, 1 H), (m, 1 H); 13 C NMR (126 MHz, CDCl 3): δ , , , 82.16, 54.21, 33.43, HRMS (ESI): C 8H 12O 3 [M+Na] + calcd: , found: Ethyl (R)-2-(2-methylbut-3-en-2-yl)-1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate. A light yellow oil (56.0 mg, 98% yield). R f = 0.34 (20:1 PE/EA). [α] 25 D = (c = 1.0, CHCl 3); 1 H NMR (500 MHz, CDCl 3): δ 8.05 (d, J = 7.9 Hz, 1 H), 7.44 (td, J = 7.5, 1.0 Hz, 1 H), (m, 1 H), 7.18 (d, J = 7.6 Hz, 1 H), 6.33 (dd, J = 17.4, 11.0 Hz, 1 H), (m, 2 H), (m, 2 H), 2.96 (ddd, J = 17.2, 12.8, 4.3 Hz, 1 H), 2.87 (ddd, J = 17.2, 4.5, 2.5 Hz, 1 H), 2.61 (ddd, J = 13.6, 4.2, 2.7 Hz, 1 H), 2.15 (td, J = 13.2, 4.9 Hz, 1 H), 1.36 (s, 3 H), 1.32 (s, 3 H), 1.11 (t, J = 7.1 Hz, 3 H); 13 C NMR (126 MHz, CDCl 3): δ , , , , , , , , , , 62.72, 61.12, 42.61, 29.10, 26.58, 24.53, 23.47, HRMS (ESI): C 18H 22O 3 [M+H] + calcd: , found: Enantiomeric excess was determined by HPLC with Chiralpak IC column (99.9 : 0.1 n-hexane : i-proh, 0.5 ml/min, 254 nm, 40 o C); t r (minor) = 24.3 min, t r (major) = 22.1 min, 85% ee. tert-butyl (R)-2-(2-methylbut-3-en-2-yl)-1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate. A yellow oil (53.4 mg, 85% yield). R f = 0.31 (20:1 PE/EA). [α] 25 D = (c = 1.0, CHCl 3); 1 H NMR (500 MHz, CDCl 3): δ 8.01 (d, J = 7.9 Hz, 1 H), 7.42 (t, J = 7.4 Hz, 1 H), 7.28 (t, J = 7.5 Hz, 1 H), 7.17 (d, J = 7.6 Hz, 1 H), 6.35 (dd, J = 17.0, 11.2 Hz, 1 H), (m, 2 H), 3.01 (ddd, J = 17.4, 12.8, 4.6 Hz, 1 H), 2.87 (ddd, J = 17.4, 4.6, 2.1 Hz, 1 H), 2.56 (ddd, J = 13.6, 4.5, 2.3 Hz, 1 H), 2.11 (td, J = 13.2, 4.9 Hz, 1 H), 1.36 (s, 3 H), 1.32 (s, 3 H), 1.28 (s, 9 H); 13 C NMR (126 MHz, CDCl 3): δ , , , , , , , , , , 82.29, 62.80, 42.11, 28.88, 27.69, 26.49, 24.46, HRMS (ESI): C 20H 26O 3 [M+Na] + calcd: , found: Enantiomeric excess was determined by HPLC with Chiralpak IG column (99:1 n-hexane:i-proh, 0.6 ml/min, 254 nm, 40 o C); t r (minor) = 8.6 min, t r (major) = 10.4 min, 92% ee.

9 8 Adamantyl (R)-2-(2-methylbut-3-en-2-yl)-1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate. A light yellow oil (72.9 mg, 93% yield). R f = 0.50 (20:1 PE/EA). [α] 25 D = (c = 0.5, CHCl 3); 1 H NMR (500 MHz, CDCl 3) δ 8.01 (d, J = 7.9 Hz, 1 H), 7.42 (t, J = 7.4 Hz, 1 H), 7.29 (dd, J = 8.7, 6.4 Hz, 1 H), 7.17 (d, J = 7.6 Hz, 1 H), 6.34 (dd, J = 17.1, 11.1 Hz, 1 H), (m, 2 H), 3.03 (ddd, J = 17.3, 12.9, 4.5 Hz, 1 H), (m, 1 H), 2.54 (ddd, J = 13.4, 4.3, 2.3 Hz, 1 H), (m, 4 H), 1.93 (dd, J = 26.3, 11.4 Hz, 6 H), 1.58 (s, 6 H), 1.37 (s, 3 H), 1.33 (s, 3 H); 13 C NMR (126 MHz, CDCl 3) δ , , , , , , , , , , 82.41, 62.96, 42.08, 41.02, 36.02, 30.71, 28.97, 26.57, HRMS (ESI): C 26H 32O 3 [M+H] + calcd: , found: Enantiomeric excess was determined by HPLC with Chiralpak IG column (99:1 n-hexane:i- PrOH, 1.0 ml/min, 254 nm, 40 o C); t r (minor) = 11.7 min, t r (major) = 10.1 min, 88% ee. Allyl (R)-2-(2-methylbut-3-en-2-yl)-1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate. A colorless oil (49.7 mg, 84% yield). R f = 0.40 (20:1 PE/EA). [α] 25 D = (c = 0.5, CHCl 3); 1 H NMR (500 MHz, CDCl 3) δ 8.06 (d, J = 7.9 Hz, 1 H), 7.44 (t, J = 7.4 Hz, 1 H), 7.30 (dd, J = 12.9, 5.4 Hz, 1 H), 7.18 (d, J = 7.6 Hz, 1 H), 6.33 (dd, J = 17.4, 10.9 Hz, 1 H), 5.74 (ddd, J = 15.8, 10.7, 5.5 Hz, 1 H), (m, 4 H), 4.55 (qd, J = 13.4, 5.5 Hz, 2 H), 2.96 (ddd, J = 17.1, 12.8, 4.3 Hz, 1 H), (m, 1 H), (m, 1 H), 2.16 (td, J = 13.2, 4.9 Hz, 1 H), 1.36 (s, 3 H), 1.32 (s, 3 H); 13 C NMR (126 MHz, CDCl 3) δ , , , , , , , , , , , , 65.47, 62.83, 42.74, 29.18, 26.59, 24.56, HRMS (ESI): C 19H 22O 3 [M+Na] + calcd: , found: Enantiomeric excess was determined by HPLC with Chiralpak IG column (99:1 n-hexane:i-proh, 1.0 ml/min, 254 nm, 40 o C); t r (minor) = 8.3 min, t r (major) = 7.6 min, 85% ee. tert-butyl (R)-7-chloro-2-(2-methylbut-3-en-2-yl)-1-oxo-1,2,3,4-tetrahydronaphthalene-2- carboxylate. A light yellow solid (68.9 mg, 99% yield). m.p o C; R f = 0.30 (20:1 PE/EA). [α] 25 D = (c = 0.5, CHCl 3); 1 H NMR (500 MHz, CDCl 3): δ 7.98 (s, 1 H), 7.38 (ddd, J = 8.1, 3.7, 1.9 Hz, 1 H), 7.13 (d, J = 8.2 Hz, 1 H), 6.31 (dd, J = 16.9, 11.1 Hz, 1 H), (m, 2 H), (m, 2 H), (m, 1 H), (m, 1 H), 1.35 (s, 3 H), 1.31 (s, 3 H), 1.30 (s, 9 H); 13 C NMR (126 MHz, CDCl 3): δ , , , , , , , , , , 82.63, 62.73, 42.15, 28.78, 27.73, 25.99, 24.40, HRMS (ESI): C 20H 25ClO 3 [M+Na] + calcd: , found: Enantiomeric excess was determined by HPLC with Chiralpak IG column (99.5:0.5 n-hexane:i-proh, 0.5 ml/min, 254 nm, 40 o C); t r (minor) = 12.2 min, t r (major) = 12.8 min, 90% ee. tert-butyl (R)-6-chloro-2-(2-methylbut-3-en-2-yl)-1-oxo-1,2,3,4-tetrahydronaphthalene-2- carboxylate. A white solid (67.5 mg, 97% yield). m.p o C; R f = 0.29 (20:1 PE/EA). [α] 25 D = (c = 0.5, CHCl 3); 1 H NMR (500 MHz, CDCl 3): δ 7.95 (d, J = 8.5 Hz, 1 H), 7.26 (dd, J = 8.4, 1.6 Hz, 1 H), 7.18 (s, 1 H), 6.31 (dd, J = 17.0, 11.1 Hz, 1 H), (m, 2 H), 2.98 (ddd, J = 17.5, 12.8,

10 9 4.6 Hz, 1 H), 2.84 (ddd, J = 17.6, 4.7, 2.3 Hz, 1 H), 2.55 (ddd, J = 13.6, 4.6, 2.4 Hz, 1 H), 2.09 (td, J = 13.2, 4.9 Hz, 1 H), 1.35 (s, 3 H), 1.31 (s, 3 H), 1.30 (s, 9 H); 13 C NMR (126 MHz, CDCl 3): δ , , , , , , , , , , 82.55, 62.77, 42.15, 28.77, 27.73, 26.38, 24.42, HRMS (ESI): C 20H 25ClO 3 [M+Na] + calcd: , found: Enantiomeric excess was determined by HPLC with Chiralpak IG column (98:2 n-hexane:i-proh, 1.0 ml/min, 254 nm, 40 o C); t r (minor) = 4.8 min, t r (major) = 7.0 min, 91% ee. tert-butyl (R)-7-bromo-2-(2-methylbut-3-en-2-yl)-1-oxo-1,2,3,4-tetrahydronaphthalene-2- carboxylate. A light yellow solid (35.4 mg, 45% yield). m.p o C; R f = 0.40 (20:1 PE/EA). [α] 25 D = (c = 0.5, CHCl 3); 1 H NMR (500 MHz, CDCl 3): δ 8.14 (d, J = 2.1 Hz, 1 H), 7.53 (dd, J = 8.1, 2.2 Hz, 1 H), 7.07 (d, J = 8.1 Hz, 1 H), 6.30 (dd, J = 17.3, 10.9 Hz, 1 H), 5.05 (dd, J = 14.2, 2.2 Hz, 2 H), 2.93 (ddd, J = 17.2, 12.6, 4.5 Hz, 1 H), 2.83 (ddd, J = 17.5, 4.8, 2.3 Hz, 1 H), 2.56 (ddd, J = 13.6, 4.5, 2.5 Hz, 1 H), 2.09 (td, J = 13.1, 5.0 Hz, 1 H), 1.35 (s, 3 H), 1.31 (d, J = 4.6 Hz, 12 H); 13 C NMR (126 MHz, CDCl 3) δ , , , , , , , , , , 82.65, 62.74, 42.17, 28.74, 27.74, 26.06, 24.40, HRMS (ESI): C 20H 25BrO 3 [M+Na] + calcd: , found: Enantiomeric excess was determined by HPLC with Chiralpak IG column (100:0 n-hexane:i-proh, 0.8 ml/min, 254 nm, 40 o C); t r (minor) = 6.1 min, t r (major) = 6.4 min, 88% ee. tert-butyl (R)-7-methoxy-2-(2-methylbut-3-en-2-yl)-1-oxo-1,2,3,4-tetrahydronaphthalene-2- carboxylate. A light yellow oil (68.1 mg, 99% yield). R f = 0.30 (20:1 PE/EA). [α] 25 D = (c = 0.5, CHCl 3); 1 H NMR (500 MHz, CDCl 3): δ 7.50 (d, J = 2.5 Hz, 1 H), 7.07 (d, J = 8.4 Hz, 1 H), 7.00 (dd, J = 8.4, 2.5 Hz, 1 H), 6.33 (dd, J = 16.9, 11.2 Hz, 1 H), (m, 2 H), 3.82 (s, 3 H), 2.93 (ddd, J = 17.1, 12.8, 6.5 Hz, 1 H), 2.80 (dd, J = 17.1, 2.5 Hz, 1 H), (m, 1 H), (m, 1 H), 1.35 (s, 3 H), 1.31 (s, 3 H), 1.29 (s, 9 H); 13 C NMR (126 MHz, CDCl 3): δ , , , , , , , , , , 82.29, 62.70, 55.40, 42.10, 29.13, 27.73, 25.69, 24.47, HRMS (ESI): C 21H 28O 4 [M+Na] + calcd: , found: Enantiomeric excess was determined by HPLC with Chiralpak IG column (99:1 n-hexane:i-proh, 0.5 ml/min, 254 nm, 40 o C); t r (minor) = 13.7 min, t r (major) = 15.8 min, 86% ee. tert-butyl (R)-6-methoxy-2-(2-methylbut-3-en-2-yl)-1-oxo-1,2,3,4-tetrahydronaphthalene-2- carboxylate. A light yellow oil (68.1 mg, 99% yield). R f = 0.28 (20:1 PE/EA). [α] 25 D = (c = 0.5, CHCl 3); 1 H NMR (500 MHz, CDCl 3): δ 7.99 (d, J = 8.8 Hz, 1 H), 6.81 (dd, J = 8.8, 2.4 Hz, 1 H), 6.62 (d, J = 2.2 Hz, 1 H), 6.34 (dd, J = 16.7, 11.2 Hz, 1 H), (m, 2 H), 3.84 (s, 3 H), 2.96 (ddd, J = 17.3, 12.9, 4.5 Hz, 1 H), 2.81 (ddd, J = 17.3, 4.5, 2.4 Hz, 1 H), 2.52 (ddd, J = 13.4, 4.4, 2.5 Hz, 1 H), 2.09 (td, J = 13.2, 4.8 Hz, 1 H), 1.35 (s, 3 H), 1.31 (s, 12 H); 13 C NMR (126 MHz, CDCl 3): δ , , , , , , , , , , 82.15, 62.61, 55.35, 42.23,

11 , 27.78, 26.94, 24.57, HRMS (ESI): C 21H 28O 4 [M+Na] + calcd: , found: Enantiomeric excess was determined by HPLC with Chiralpak IG column (98:2 n-hexane:i-proh, 1.0 ml/min, 254 nm, 40 o C); t r (minor) = 9.1 min, t r (major) = 17.2 min, 82% ee. tert-butyl (R)-5-methoxy-2-(2-methylbut-3-en-2-yl)-1-oxo-1,2,3,4-tetrahydronaphthalene-2- carboxylate. A light yellow oil (68.1 mg, 99% yield). R f = 0.30 (20:1 PE/EA). [α] 25 D = (c = 0.5, CHCl 3); 1 H NMR (500 MHz, CDCl 3): δ 7.61 (d, J = 7.9 Hz, 1 H), 7.26 (dd, J = 15.1, 7.1 Hz, 1 H), 6.96 (d, J = 8.0 Hz, 1 H), 6.35 (dd, J = 17.0, 11.1 Hz, 1 H), 5.05 (dd, J = 9.3, 8.1 Hz, 2 H), 3.85 (s, 3 H), 3.01 (ddd, J = 18.2, 5.1, 1.9 Hz, 1 H), (m, 1 H), 2.59 (ddd, J = 13.6, 5.0, 2.0 Hz, 1 H), (m, 1 H), 1.37 (s, 3 H), 1.32 (s, 3 H), 1.25 (s, 9 H); 13 C NMR (126 MHz, CDCl 3): δ , , , , , , , , , , 82.16, 62.37, 55.63, 41.87, 27.93, 27.67, 24.40, 23.40, HRMS (ESI): C 21H 28O 4 [M+Na] + calcd: , found: Enantiomeric excess was determined by HPLC with Chiralpak IG column (98:2 n-hexane:i-proh, 1.0 ml/min, 254 nm, 40 o C); t r (minor) = 5.7 min, t r (major) = 6.9 min, 89% ee. tert-butyl (R)-2-(2-methylbut-3-en-2-yl)-1-oxo-6-phenyl-1,2,3,4-tetrahydronaphthalene-2- carboxylate. A light yellow solid (75.7 mg, 97% yield). m.p o C; R f = 0.40 (20:1 PE/EA). [α] 25 D = (c = 0.5, CHCl 3); 1 H NMR (500 MHz, CDCl 3): δ 8.11 (d, J = 8.2 Hz, 1 H), (m, 2 H), 7.55 (d, J = 8.2 Hz, 1 H), 7.47 (t, J = 7.6 Hz, 2 H), (m, 2 H), 6.39 (dd, J = 17.0, 11.1 Hz, 1 H), (m, 2 H), 3.08 (ddd, J = 17.2, 12.8, 4.5 Hz, 1 H), 2.95 (ddd, J = 17.3, 4.5, 2.2 Hz, 1 H), 2.61 (ddd, J = 13.5, 4.4, 2.4 Hz, 1 H), 2.17 (td, J = 13.2, 4.8 Hz, 1 H), 1.40 (s, 3 H), 1.36 (s, 3 H), 1.34 (s, 9 H); 13 C NMR (126 MHz, CDCl 3): δ , , , , , , , , , , , , , , 82.38, 62.93, 42.24, 29.10, 27.79, 26.76, 24.66, HRMS (ESI): C 26H 30O 3 [M+Na] + calcd: , found: Enantiomeric excess was determined by HPLC with Chiralpak IG column (98:2 n-hexane:i-proh, 1.0 ml/min, 254 nm, 40 o C); t r (minor) = 8.4 min, t r (major) = 14.7 min, 87% ee. tert-butyl (R)-2-(2-methylbut-3-en-2-yl)-1-oxo-6-(phenylethynyl)-1,2,3,4-tetrahydronaphthalene-2- carboxylate. A light yellow oil (78.7 mg, 95% yield). R f = 0.30 (20:1 PE/EA). [α] 25 D = (c = 0.5, CHCl 3); 1 H NMR (500 MHz, CDCl 3) δ 8.01 (d, J = 8.1 Hz, 1 H), (m, 2 H), 7.45 (d, J = 8.2 Hz, 1 H), 7.38 (dd, J = 6.3, 2.7 Hz, 4 H), 6.35 (dd, J = 17.0, 11.2 Hz, 1 H), (m, 2 H), 3.01 (ddd, J = 17.4, 12.7, 4.6 Hz, 1 H), 2.88 (ddd, J = 17.4, 4.6, 2.1 Hz, 1 H), 2.58 (ddd, J = 13.6, 4.5, 2.3 Hz, 1 H), 2.12 (td, J = 13.2, 4.9 Hz, 1 H), 1.38 (s, 3 H), 1.34 (s, 3 H), 1.30 (s, 9 H); 13 C NMR (126 MHz, CDCl 3) δ , , , , , , , , , , , , , , 92.22, 88.86, 82.50, 62.85, 42.16, 28.77, 27.74, 26.31, 24.46, HRMS (ESI):

12 11 C 28H 30O 3 [M+Na] + calcd: , found: Enantiomeric excess was determined by HPLC with Chiralpak IG column (98:2 n-hexane:i-proh, 1.0 ml/min, 254 nm, 40 o C); t r (minor) = 8.4 min, t r (major) = 9.3 min, 92% ee. tert-butyl (R)-2-(2-methylbut-3-en-2-yl)-1-oxo-2,3-dihydro-1H-indene-2-carboxylate. A light yellow solid (49.8 mg, 83% yield). m.p o C; R f = 0.28 (20:1 PE/EA). [α] 25 D = -4.4 (c = 0.5, CHCl 3); 1 H NMR (400 MHz, CDCl 3): δ 7.75 (d, J = 7.7 Hz, 1 H), 7.58 (td, J = 7.6, 1.1 Hz, 1 H), (m, 2 H), 6.20 (dd, J = 17.4, 10.8 Hz, 1 H), 5.03 (ddd, J = 11.9, 9.9, 1.2 Hz, 2 H), 3.49 (d, J = 17.7 Hz, 1 H), 3.27 (d, J = 17.7 Hz, 1 H), 1.40 (s, 9 H), 1.34 (s, 3 H), 1.22 (s, 3 H); 13 C NMR (126 MHz, CDCl 3): δ , , , , , , , , , , 81.94, 65.60, 42.41, 36.39, 27.87, 23.64, HRMS (ESI): C 19H 24O 3 [M+Na] + calcd: , found: Enantiomeric excess was determined by HPLC with Chiralpak IG column (99:1 n-hexane:i-proh, 0.6 ml/min, 254 nm, 40 o C); t r (minor) = 12.4 min, t r (major) = 11.0 min, 75% ee. tert-butyl (R)-5-bromo-2-(2-methylbut-3-en-2-yl)-1-oxo-2,3-dihydro-1H-indene-2-carboxylate. A light yellow solid (70.5 mg, 93% yield). m.p o C; R f = 0.31 (20:1 PE/EA). [α] 25 D = (c = 0.5, CHCl 3); 1 H NMR (500 MHz, CDCl 3): δ (dd, J = 4.3, 3.6 Hz, 2 H), (m, 1 H), 6.14 (dd, J = 17.4, 10.8 Hz, 1 H), 5.03 (ddd, J = 10.8, 8.6, 1.1 Hz, 2 H), 3.47 (d, J = 17.9 Hz, 1 H), 3.24 (d, J = 17.9 Hz, 1 H), 1.40 (s, 9 H), 1.32 (s, 3 H), 1.21 (s, 3 H); 13 C NMR (126 MHz, CDCl 3): δ , , , , , , , , , , 82.25, 65.70, 42.51, 36.00, 27.87, 23.55, HRMS (ESI): C 19H 23BrO 3 [M+Na] + calcd: , found: Enantiomeric excess was determined by HPLC with Chiralpak IG column (99:1 n-hexane:i-proh, 1.0 ml/min, 254 nm, 40 o C); t r (minor) = 11.5 min, t r (major) = 6.8 min, 66% ee. tert-butyl (R)-6-(2-methylbut-3-en-2-yl)-5-oxo-6,7,8,9-tetrahydro-5H-benzo[7]annulene-6- carboxylate. A yellow oil (34.1 mg, 52% yield). R f = 0.38 (20:1 PE/EA). [α] 25 D = (c = 0.5, CHCl 3); 1 H NMR (500 MHz, CDCl 3): δ 7.39 (dd, J = 7.6, 1.3 Hz, 1 H), 7.32 (td, J = 7.4, 1.4 Hz, 1 H), 7.25 (t, J = 7.2 Hz, 1 H), 7.08 (d, J = 7.5 Hz, 1 H), 6.40 (dd, J = 17.5, 10.9 Hz, 1 H), (m, 2 H), 2.98 (ddd, J = 15.7, 11.6, 4.1 Hz, 1 H), (m, 1 H), 2.43 (ddd, J = 13.8, 7.6, 4.8 Hz, 1 H), 2.07 (tt, J = 14.2, 4.8 Hz, 1 H), 1.94 (ddd, J = 13.6, 7.6, 3.5 Hz, 1 H), (m, 1 H), 1.29 (s, 3 H), 1.26 (s, 9 H), 1.23 (s, 3 H); 13 C NMR (126 MHz, CDCl 3): δ , , , , , , , , , , 81.92, 67.15, 44.19, 32.48, 29.38, 27.59, 24.50, 24.44, HRMS (ESI): C 21H 28O 3 [M+Na] + calcd: , found: Enantiomeric excess was determined by HPLC with Chiralpak IC column (99:1 n-hexane:i-proh, 1.0 ml/min, 254 nm, 40 o C); t r (minor) = 5.9 min, t r (major) = 8.5 min, 86% ee.

13 12 Ethyl (R)-1-oxo-2-(1-vinylcyclobutyl)-1,2,3,4-tetrahydronaphthalene-2-carboxylate. A colorless oil (51.3 mg, 86% yield). R f = 0.32 (20:1 PE/EA). [α] 25 D = (c = 1.0, CHCl 3); 1 H NMR (500 MHz, CDCl 3): δ (m, 1 H), 7.44 (td, J = 7.5, 1.2 Hz, 1 H), (m, 1 H), 7.18 (d, J = 7.6 Hz, 1 H), 6.21 (dd, J = 17.4, 10.7 Hz, 1 H), 5.25 (ddd, J = 14.0, 11.7, 1.0 Hz, 2 H), 4.16 (q, J = 7.1 Hz, 2 H), 2.98 (ddd, J = 16.7, 11.8, 4.5 Hz, 1 H), 2.87 (dt, J = 17.3, 4.2 Hz, 1 H), 2.56 (dd, J = 21.0, 9.4 Hz, 1 H), (m, 2 H), (m, 2 H), (m, 1 H), (m, 1 H), (m, 1 H), 1.15 (t, J = 7.1 Hz, 3 H); 13 C NMR (126 MHz, CDCl 3) : δ , , , , , , , , , , 62.56, 61.23, 49.26, 29.94, 28.39, 27.46, 26.33, 15.86, HRMS (ESI): C 19H 22O 3 [M+H] + calcd: , found: Enantiomeric excess was determined by HPLC with Chiralpak IG column (99:1 n-hexane:i-proh, 0.8 ml/min, 254 nm, 40 o C); t r (minor) = 11.4 min, t r (major) = 12.2 min, 48% ee. Ethyl (R)-1-oxo-2-(1-vinylcyclohexyl)-1,2,3,4-tetrahydronaphthalene-2-carboxylate. A white solid (30.6 mg, 47% yield). m.p o C; R f = 0.38 (20:1 PE/EA). [α] 25 D = (c = 0.5, CHCl 3); 1 H NMR (500 MHz, CDCl 3): δ 8.03 (dd, J = 7.9, 1.0 Hz, 1 H), 7.42 (td, J = 7.5, 1.4 Hz, 1 H), 7.29 (dd, J = 8.8, 6.3 Hz, 1 H), 7.16 (d, J = 7.6 Hz, 1 H), 5.95 (dd, J = 17.9, 11.2 Hz, 1 H), 5.29 (dd, J = 11.2, 1.1 Hz, 1 H), 5.03 (dd, J = 18.1, 1.3 Hz, 1 H), (m, 2 H), (m, 2 H), 2.64 (ddd, J = 31.8, 18.8, 15.4 Hz, 2 H), 2.18 (ddd, J = 13.3, 12.1, 5.6 Hz, 1 H), 2.03 (s, 1 H), 1.84 (d, J = 12.2 Hz, 1 H), 1.63 (s, 1 H), 1.50 (ddt, J = 17.0, 7.5, 6.4 Hz, 5 H), (m, 1 H), 1.10 (t, J = 7.1 Hz, 3 H); 13 C NMR (126 MHz, CDCl 3): δ , , , , , , , , , , , 46.64, 29.70, 28.13, 26.65, 26.15, 22.56, HRMS (ESI): C 21H 26O 3 [M+Na] + calcd: , found: Enantiomeric excess was determined by HPLC with Chiralpak IG column (99:1 n-hexane:i-proh, 0.8 ml/min, 254 nm, 40 o C); t r (minor) = 16.5 min, t r (major) = 11.9 min, 51% ee. Ethyl 2-(3,7-dimethylocta-1,6-dien-3-yl)-1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate. A colorless oil (59.5 mg, 84% yield). R f = 0.32 (20:1 PE/EA). 1 H NMR (500 MHz, CDCl 3): δ 8.04 (ddd, J = 12.4, 7.9, 1.0 Hz, 1 H), 7.43 (tdd, J = 7.5, 4.1, 1.3 Hz, 1 H), (m, 1 H), (m, 1 H), 6.32 (s, 0.55 H), 6.09 (dd, J = 17.6, 10.9 Hz, 0.38 H), (m, 3 H), (m, 2 H), (m, 2 H), (m, 1 H), 2.37 (s, 1 H), (m, 0.5 H), (m, 1.5 H), 1.67 (d, J = 4.2 Hz, 3 H), 1.60 (d, J = 5.5 Hz, 3 H), (m, 1 H), 1.31 (s, 1 H), 1.26 (s, 2 H), 1.09 (td, J = 7.1, 4.5 Hz, 3 H); 13 C NMR (126 MHz, CDCl 3) : δ , , , , , , , , , , , , , , , , , , , , , , , , 63.40, 61.09, 46.24, 46.17, 35.91, 29.45, 28.71, 26.68,

14 , 25.68, 25.67, 23.40, 23.11, 17.83, 17.64, 17.61, 17.24, HRMS (ESI): C 23H 30O 3 [M+H] + calcd: , found: (3R,4R)-4-Vinyl-3',4,4',5-tetrahydro-1'H,2H-spiro[furan-3,2'-naphthalene]-1',2-dione. A white solid (38.7 mg, 80% yield). m.p o C; R f = 0.38 (5:1 PE/EA). [α] 25 D = (c = 1.0, CHCl 3); 1 H NMR (500 MHz, CDCl 3): δ 8.04 (dd, J = 7.9, 0.7 Hz, 1 H), 7.53 (td, J = 7.5, 1.3 Hz, 1 H), 7.34 (t, J = 7.6 Hz, 1 H), 7.25 (d, J = 7.7 Hz, 1 H), 5.55 (dt, J = 16.9, 9.7 Hz, 1 H), 5.33 (d, J = 16.8 Hz, 1 H), 5.03 (dd, J = 10.1, 0.9 Hz, 1 H), 4.39 (t, J = 8.5 Hz, 1 H), 4.27 (dd, J = 10.7, 9.0 Hz, 1 H), 3.34 (dd, J = 19.2, 8.8 Hz, 1 H), (m, 2 H), 2.77 (ddd, J = 13.8, 11.3, 5.5 Hz, 1 H), 2.23 (dt, J = 13.8, 4.5 Hz, 1 H); 13 C NMR (126 MHz, CDCl 3) δ , , , , , , , , , , 69.20, 58.08, 52.52, 31.80, HRMS (ESI): C 15H 14O 3 [M+Na] + calcd: , found: Enantiomeric excess was determined by HPLC with Chiralpak IG column (85:15 n-hexane:i- PrOH, 1.0 ml/min, 254 nm, 40 o C); t r (minor) = 16.2 min, t r (major) = 14.7 min, 94% ee. (3R,4S)-4-Vinyl-3',4,4',5-tetrahydro-1'H,2H-spiro[furan-3,2'-naphthalene]-1',2-dione. A colorless oil (7.7 mg, 16% yield). R f = 0.40 (5:1 PE/EA). [α] 25 D = (c = 1.0, CHCl 3); 1 H NMR (500 MHz, CDCl 3): δ 8.07 (d, J = 7.9 Hz, 1 H), 7.54 (td, J = 7.5, 1.3 Hz, 1 H), 7.35 (t, J = 7.6 Hz, 1 H), 7.28 (d, J = 8.0 Hz, 1 H), 5.82 (ddd, J = 19.0, 13.6, 9.1 Hz, 1 H), (m, 2 H), 4.57 (dd, J = 9.0, 6.9 Hz, 1 H), 4.19 (dd, J = 9.0, 5.9 Hz, 1 H), 3.79 (dd, J = 15.2, 6.4 Hz, 1 H), 3.22 (ddd, J = 17.1, 8.3, 4.7 Hz, 1 H), 3.00 (ddd, J = 17.1, 7.3, 4.7 Hz, 1 H), 2.46 (ddd, J = 13.9, 7.4, 4.7 Hz, 1 H), (m, 1 H); 13 C NMR (126 MHz, CDCl 3): δ , , , , , , , , , , 69.88, 57.36, 45.85, 25.96, HRMS (ESI): C 15H 14O 3 [M+Na] + calcd: , found: Enantiomeric excess was determined by HPLC with Chiralpak IG column (85:15 n-hexane:i-proh, 1.0 ml/min, 254 nm, 40 o C); t r (minor) = 15.5 min, t r (major) = 17.4 min, 70% ee. Ethyl (R)-2-((R)-oct-1-en-3-yl)-1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate. A colorless oil (56.4 mg, 86% yield). R f = 0.38 (20:1 PE/EA). [α] 25 D = (c = 0.5, CHCl 3); 1 H NMR (500 MHz, CDCl 3): δ (m, 1 H), 7.45 (td, J = 7.5, 1.4 Hz, 1 H), 7.31 (dd, J = 15.5, 7.9 Hz, 1 H), 7.20 (d, J = 7.7 Hz, 1 H), 5.92 (dt, J = 17.1, 9.9 Hz, 0.2 H), 5.69 (dt, J = 17.0, 10.1 Hz, 0.8 H), (m, 2 H), (m, 2 H), 3.20 (ddd, J = 17.2, 12.4, 4.6 Hz, 0.8 H), (m, 0.2 H), (m, 1.8 H), (m, 0.2 H), (m, 1 H), (m, 1 H), (m, 1 H), (m, 7 H), 1.16 (td, J = 7.1, 4.0 Hz, 3 H), 0.87 (dt, J = 7.2, 3.2 Hz, 3 H); 13 C NMR (126 MHz, CDCl 3): δ , , , , , , , , , , , , , , , , , , , , 61.39, 61.23, 61.20, 61.12, 49.80, 49.38, 31.61, 30.58, 29.86, 29.17, 28.34, 27.81, 27.59, 26.32, 26.24, 22.59, 22.57, 14.09,

15 HRMS (ESI): C 21H 28O 3 [M+H] + calcd: , found: Enantiomeric excess was determined by HPLC with Chiralpak IG column (99.9:0.1 n-hexane:i-proh, 0.3 ml/min, 254 nm, 40 o C); t r (minor 1) = 52.5 min, t r (major 1) = 41.9 min, t r (minor 2) = 47.2 min, t r (major 2) = 54.7 min, minor: 67% ee, major: 94% ee. 14

16 15 7. X-Ray Data for Compound 3k, 3s and Co(dppbz)2Cl X-Ray data for compound 3k Empirical formula C 26H 28O 3 Formula weight CCDC Number Crystal habit, colour block, colorless Crystal size, mm Temperature, K 296(2) Wavelength, λ (Å) Crystal system Orthorhombic Space group P2(1)2(1)2 Unit cell dimensions a = (5) Å alpha = 90 deg b = (8) Å beta = 90 deg c = (3) Å gamma = 90 deg Volume, V (Å 3 ) (15) Z 4 Calculated density, mg m Absorption coefficient, µ (mm 1 ) F(000) 832 range for data collection to deg Limiting indices 15 h 15, 27 k 27, 9 l 8 Reflection collected/unique / 4103 [R(int) = ] Completeness to % Refinement method Full-matrix least-squares on F^2 Data/restraints/parameters 4103 / 1 / 269 Goodness of fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e Å 3

17 16 X-Ray data for compound 3s Empirical formula C 15H 14O 3 Formula weight CCDC Number Crystal habit, colour block, colorless Crystal size, mm Temperature, K 173(2) Wavelength, λ (Å) Crystal system Orthorhombic Space group P2(1)2(1)2(1) Unit cell dimensions a = (3) Å alpha = 90 deg b =8.1537(3) Å beta = 90 deg c = (6) Å gamma = 90 deg Volume, V (Å 3 ) (8) Z 4 Calculated density, mg m Absorption coefficient, mm F(000) 512 range for data collection to deg Limiting indices 7 h 7, 9 k 9, 27 l 26 Reflection collected/unique / 2174 [R(int) = ] Completeness to % Max. and min. transmission , Refinement method Full-matrix least-squares on F^2 Data/restraints/parameters 2174 / 0 / 163 Goodness of fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e Å 3

18 17 X-Ray data for complex Co(dppbz) 2Cl Empirical formula C 60H 48ClCoP 4 Formula weight CCDC Number Crystal size, mm Temperature, K 297(2) Wavelength, λ (Å) Crystal system Triclinic Space group P-1 Unit cell dimensions a = (12) Å alpha = (5) deg. b = (13) Å beta = (4) deg c = (2) Å gamma = (4) deg Volume, V (Å 3 ) (5) Z 2 Calculated density, mg m Absorption coefficient, mm F(000) 1024 range for data collection to deg Limiting indices -13<=h<=13, -14<=k<=14, -24<=l<=24 Reflection collected/unique / 8365 [R(int) = ] Completeness to % Refinement method Full-matrix least-squares on F^2 Data/restraints/parameters 8365 / 0 / 595 Goodness of fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e Å 3

19 8. NMR Spectra 18

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43 42 1 H-NMR (500MHz, CD3CN) spectra of Co(dppbz)2Cl 31 P-NMR (500MHz, CD3CN) spectra of Co(dppbz)2Cl

44 31 P-NMR (500MHz, CD3CN) spectra of Co(dppbz)2Cl and NaBARF 43

45 9. HPLC Results 44

46 45

47 46

48 47

49 48

50 49

51 50

52 51

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64 63

65 References [1] Jones, S.; Zhao, P. Tetrahedron: Asymmetry. 2014, 25, [2] Chen, M.; Huang, Z-T.; Zheng, Q-Y. Org. Biomol. Chem. 2015, 13, [3] Rambla, M.; Duroure, L.; Chabaud, L.; Guillou, C. Eur. J. Org. Chem. 2014, [4] Li, C.; Breit, B. Chem. Eur. J. 2016, 22, [5] Weiss, M.; Holz, J.; Peters, R. Eur. J. Org. Chem. 2016, [6] Spino, C.; Tremblay, M-C.; Gobdout, C. Org. Lett. 2004, 6,