Synlett 2017; 28(14): 1801-1806
DOI: 10.1055/s-0036-1589033
letter
© Georg Thieme Verlag Stuttgart · New York

Thieme Chemistry Journals Awardees – Where Are They Now?
Chiral Sulfinamide Ligands and Pd-Catalyzed Asymmetric Allylic Alkylations of Ethyl 2-Fluoroacetoacetate

Mingzhu Zhao
a   Shanghai Key Lab of Chemical Assessment and Sustainability, School of Chemical Science and Engineering, Tongji University, Shanghai 200092, P. R. of China   Email: xmzhao08@mail.tongji.edu.cn
,
Yawei Tian
a   Shanghai Key Lab of Chemical Assessment and Sustainability, School of Chemical Science and Engineering, Tongji University, Shanghai 200092, P. R. of China   Email: xmzhao08@mail.tongji.edu.cn
,
Xiaoming Zhao*
a   Shanghai Key Lab of Chemical Assessment and Sustainability, School of Chemical Science and Engineering, Tongji University, Shanghai 200092, P. R. of China   Email: xmzhao08@mail.tongji.edu.cn
b   Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, P. R. of China
› Author Affiliations
Supported by: National Science Foundation of China 21272175
Supported by: Shanghai Science and Technology Commission 14DZ2261100
Further Information

Publication History

Received: 16 March 2017

Accepted after revision: 18 April 2017

Publication Date:
08 May 2017 (online)


Abstract

New chiral sulfinamide ligands made from salicylic acids and chiral tert-butanesulfinamide was utilized in Pd-catalyzed asymmetric allylic substitutions of ethyl 2-fluoroacetoacetate, which afforded the fluorinated allyl products with up to 98% yield, 94% ee, and 2.2:1 dr. Both sulfoxide and hydroxyl group on the sulfanilamide ligands are ­crucial for enantiocontrol in the Pd-catalyzed allylic alkylations of ethyl 2-fluoroacetoacetate.

Supporting Information

 
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  • 22 Typical Procedure for the Synthesis of (R)-L1 To a solution of salicylic acid (1.0 mmol) in THF (2.0 mL) was added 1,1′-carbonyldiimidazole (CDI; 1.0 mmol, 1.0 equiv) slowly at room temperature, then the reaction mixture was heated to 50 °C for 1.0 h. The solution was cooled to room temperature and concentrated to give the active amide. To a suspension of KH (30% in oil, 2.0 mmol, 2.0 equiv) in THF (5.0 mL) was added (R)-tert-butanesulfinamide (1.0 mmol) under argon at room temperature and the mixture was stirred for 0.5 h. The active amide was added and the mixture was stirred at 50 °C for 1.0 h. The reaction mixture was cooled to room temperature and acidified with aqueous HCl to pH >7, then the mixture was diluted with EtOAc (10 mL), washed with H2O (3 × 10 mL) and brine (10 mL), dried over anhydrous Na2SO4, filtered, and concentrated under vacuum. The residue was purified by column chromatography on silica gel (EtOAc) to give the desired product (R)-L1 (149.4 mg, 62% yield) as a white solid; mp 144.6–145.9 °C; [α] d 25 –73.8 (c = 1.0, MeOH). 1H NMR (400 MHz, CDCl3): δ = 7.78 (d, J = 7.8 Hz, 1 H), 7.39 (t, J = 7.4 Hz, 1 H), 7.01 (d, J = 8.1 Hz, 1 H), 6.88 (t, J = 7.5 Hz, 1 H), 1.36 (s, 9 H). 13C NMR (100 MHz, CDCl3): δ = 168.94, 159.16, 135.22, 129.55, 119.79, 118.01, 115.40, 57.05, 22.26. IR (KBr): 3259, 2963, 2930, 2854, 1677, 1605, 1464, 1408, 1393, 1304, 1232, 1107, 1032 cm–1. HRMS (ESI-TOF): m/z [M + H]+ calcd for C11H16NO3S: 242.0845; found: 242.0841
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  • 27 Typical Procedure for Pd-Catalyzed Allylic Alkylation Reaction [Pd(C3H5)Cl]2 (0.004 mmol, 4 mol%), (R)-L1 (0.008 mmol, 8 mol%), and (E)-1,3-disubstituted allyl acetate 1 (0.1 mmol) were dissolved in THF/dioxane (2.0 mL, 1:1) in a dry Schlenk tube filled with argon. The reaction mixture was stirred for 30 min at room temperature, then ethyl 2-fluoroacetoacetate (2a; 0.3 mmol, 3.0 equiv) and K3PO4 (0.3 mmol, 3.0 equiv) were added. The reaction mixture was stirred at room temperature and the progress of the reaction was monitored by TLC. Upon completion, the mixture was filtered through Celite and the solvent was evaporated under vacuum. The residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate) to give the desired products 3ai. (E)-Ethyl 2-Acetyl-3,5-bis(3-chlorophenyl)-2-fluoropent-4-enoate (3a): Colorless oil (39.8 mg, 98% yield). The diastereomeric ratio was 1.6:1 determined by 1H NMR spectroscopic analysis. The ee value of the major diastereomer was 80%, the minor diastereomer was 78%, determined by chiral HPLC [Daicel CHIRALCEL OJ-H (0.46 cm × 25 cm); hexane/i-PrOH = 98:2; flow rate = 1.0 mL/min; detection wavelength = 254 nm; tR (major) = 16.984, 19.423 min; tR (minor) = 21.968, 25.166 min]. 1H NMR (400 MHz, CDCl3, stereoisomeric mixture): δ = 7.42–7.17 (m, 13 H), 6.61–6.21 (m, 3.3 H), 4.52 (dd, J = 32.6, 8.8 Hz, 1.6 H), 4.37–4.16 (m, 2 H), 4.06 (m, 1.3 H), 2.32 (d, J = 5.7 Hz, 1.9 H), 2.01 (d, J = 5.6 Hz, 3 H), 1.27 (t, J = 7.1 Hz, 3 H), 1.06 (t, J = 7.1 Hz, 1.9 H). 13C NMR (100 MHz, CDCl3, stereoisomeric mixture): δ = 201.32 (d, J = 29.8 Hz), 201.14 (d, J = 29.9 Hz), 164.66 (d, J = 25.7 Hz), 164.26 (d, J = 25.9 Hz), 139.01, 138.42, 138.10, 138.03, 134.60, 134.46, 133.61, 133.30, 130.04, 130.02, 129.85, 129.52 (d, J = 2.5 Hz), 129.19 (d, J = 2.6 Hz), 128.11, 128.06, 128.05, 128.00, 127.70 (d, J = 2.2 Hz), 127.12 (d, J = 2.6 Hz), 126.38, 126.33, 125.79, 125.75, 125.60, 125.55, 124.89, 124.80, 102.68 (d, J = 206.1 Hz), 102.52 (d, J = 207.9 Hz), 63.09, 62.84, 52.88 (d, J = 18.1 Hz), 52.82 (d, J = 18.2 Hz), 26.85, 26.84, 14.18, 13.77. 19F NMR (376 MHz, CDCl3, stereoisomeric mixture): δ = –174.49, –175.05. IR (KBr): 3064, 2982, 2932, 2854, 1754, 1734, 1594, 1570, 1476, 1431, 1356, 1246, 1205, 967, 913, 781, 742 cm–1. HRMS (ESI-TOF): m/z [M + Na]+ calcd. for C21H19Cl2FNaO3: 431.0587; found: 431.0592

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