Enantioselective Synthesis of Tertiary Trifluoromethyl Carbinols by Vinylogous Aldol Reaction of 3-Methylcyclohex-2-en-1-one with (Het)aryl Trifluoromethyl Ketones

Fenfen Chen; Zhixin Chang; Chigumbu Paidamoyo; Xiaofei Zeng; Yongjiang Wang; Xiaoyu Han

doi:10.1055/s-0037-1611363

Synlett, Table of Contents

Synlett 2019; 30(02): 240-244
DOI: 10.1055/s-0037-1611363

letter

Enantioselective Synthesis of Tertiary Trifluoromethyl Carbinols by Vinylogous Aldol Reaction of 3-Methylcyclohex-2-en-1-one with (Het)aryl Trifluoromethyl Ketones

Authors

Fenfen Chen ◊

^aZhejiang Provincial Key Laboratory for Chemical and Biological Processing Technology of Farm Products, School of Biological and Chemical Engineering, Zhejiang University of Science and Technology, Hangzhou 310023, P. R. of China Email: chemhanxy@zust.edu.cn
Zhixin Chang ◊

^aZhejiang Provincial Key Laboratory for Chemical and Biological Processing Technology of Farm Products, School of Biological and Chemical Engineering, Zhejiang University of Science and Technology, Hangzhou 310023, P. R. of China Email: chemhanxy@zust.edu.cn
Chigumbu Paidamoyo

^aZhejiang Provincial Key Laboratory for Chemical and Biological Processing Technology of Farm Products, School of Biological and Chemical Engineering, Zhejiang University of Science and Technology, Hangzhou 310023, P. R. of China Email: chemhanxy@zust.edu.cn
Xiaofei Zeng

^bCollege of Materials, Chemistry, and Chemical Engineering, Hangzhou Normal University, Hangzhou 310036, P. R. of China
Yongjiang Wang

^aZhejiang Provincial Key Laboratory for Chemical and Biological Processing Technology of Farm Products, School of Biological and Chemical Engineering, Zhejiang University of Science and Technology, Hangzhou 310023, P. R. of China Email: chemhanxy@zust.edu.cn
Xiaoyu Han*

^aZhejiang Provincial Key Laboratory for Chemical and Biological Processing Technology of Farm Products, School of Biological and Chemical Engineering, Zhejiang University of Science and Technology, Hangzhou 310023, P. R. of China Email: chemhanxy@zust.edu.cn

Abstract

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^◊ These authors contributed equally to this work.

Abstract

A direct enantioselective vinylogous aldol reaction of trifluoromethyl ketones with 3-methylcyclohex-2-en-1-one through hydrogen-bond-directing dienamine catalysis by a diamine–sulfonamide catalyst has been demonstrated. A range of trifluoromethylated tertiary alcohols were efficiently produced in yields of up to 86% and with 93% enantioselectivity.

Key words

organocatalysis - enantioselectivity - vinylogous aldol reaction - asymmetric catalysis - trifluorohydroxypropylcyclohexenones - aryl trifluoromethyl ketones

Full Text

References

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24 3-[(2R)-3,3,3-Trifluoro-2-hydroxy-2-phenylpropyl]cyclohex-2-en-1-one (3a); Typical Procedure Catalyst 12 (0.02 mmol, 20 mol%) was added to a stirred solution of PhCOCF₃ (2a; 0.3 mmol, 3.0 equiv), 3-methylcyclohex-2-en-1-one (1a; 0.1 mmol, 1.0 equiv), and BzOH (0.05 mmol, 0.5 equiv) in Et₂O (1 mL), and the resulting mixture was stirred at r.t. until the starting material disappeared (TLC). The mixture was then directly purified by column chromatography [silica gel, hexane–EtOAc (15:1 to 10:1)] to give a white solid; yield: 22.4 mg (79%, 73% ee); mp 151.3–152.1 °C;[α]_D ²⁰ –8.22 (c 1.0, CHCl₃). ¹H NMR (500 MHz, CDCl₃): δ = 7.55 (d, J = 7.4 Hz, 2 H), 7.43–7.33 (m, 3 H), 5.83 (s, 1 H), 3.40 (s, 1 H), 3.07–2.97 (m, 2 H), 2.25–2.17 (m, 2 H), 2.15 –2.09 (m, 1 H), 1.90–1.84 (m, 1 H), 1.79–1.72 (m, 2 H). ¹³C NMR (126 MHz, CDCl₃): δ = 199.7, 159.1, 136.0, 130.7, 128.9, 128.5, 126.1, 125.3 (q, J = 286.4 Hz), 76.8 (q, J = 28.1 Hz), 43.8, 37.0, 30.9, 22.6. ¹⁹F NMR (470 MHz, CDCl₃): δ = –79.6. HRMS: m/z [M + H]⁺ calcd for C₁₅H₁₆F₃O₂ = 285.1097; found = 285.1102. HPLC (Chiralpak AD-H; λ = 254 nm; 20% i-PrOH–hexanes, flow rate = 1.0 mL/min): t_R (major) = 4.55 min, t _R (minor) = 9.96 min.

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