Highly Enantio- and Diastereoselective Synthesis of β-Methyl-γ-monofluoromethyl-Substituted Alcohols

• Published in: Chemistry : a European journal Vol. 17; no. 29; pp. 8066 - 8070
• Main Authors: Yang, Wenguo, Wei, Xinle, Pan, Yuanhang, Lee, Richmond, Zhu, Bo, Liu, Hongjun, Yan, Lin, Huang, Kuo-Wei, Jiang, Zhiyong, Tan, Choon-Hong
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 11.07.2011; WILEY‐VCH Verlag; Wiley
• Subjects: Alcohols; Alcohols - chemical synthesis; Alcohols - chemistry; Alkaloids; Alkylation; asymmetric catalysis; Carbonates; Carbonates - chemistry; Catalysis; Chemical reactions; Chemistry; Chemistry, Multidisciplinary; Cinchona - chemistry; Cinchona Alkaloids - chemistry; Derivatives; FBSM; Halogenation; Hydrocarbons, Fluorinated - chemistry; Mathematical analysis; Methane - analogs & derivatives; Methane - chemistry; Models, Molecular; Morita-Baylis-Hillman reactions; organocatalysis; Physical Sciences; Science & Technology; Stereoisomerism; Stereoselectivity; Sulfones - chemistry; Morita-Baylis-Hillman reactions; ENANTIOSELECTIVE FLUORINATION; ALLYLIC ALKYLATION; alcohols; asymmetric catalysis; QUATERNARY; MICHAEL ADDITION; organocatalysis; ASYMMETRIC MANNICH REACTION; KETO ESTERS; FBSM; CHEMISTRY; BAYLIS-HILLMAN CARBONATES; CONJUGATE ADDITION
• ISSN: 0947-6539; 1521-3765; 1521-3765
• DOI: 10.1002/chem.201100929

Enanatiopure β‐methyl‐γ‐monofluoromethyl alcohols were prepared from the allylic alkylation between fluorobis(phenylsulfonyl)methane with Morita–Baylis–Hillman carbonates. The reaction was catalyzed by using the Cinchona alkaloid derivative, (DHQD)2AQN. The origin of the stereoselectivity was verified by DFT methods. Calculated geometries and relative energies of various transition states strongly support the observed stereoselectivity. Get ‘naked’ with F: Enanatiopure β‐methyl‐γ‐monofluoromethyl alcohols were prepared from the allylic alkylation between fluorobis(phenylsulfonyl)methane with Morita–Baylis–Hillman carbonates (see scheme). The reaction was catalyzed by using the Cinchona alkaloid derivative, (DHQD)2AQN.