Cinchona-Based Primary Amine Catalyzed a Proximal Functionalization of Dienamines: Asymmetric α-Fluorination of α-Branched Enals

被引：29

作者：

Arimitsu, Satoru ^{[1
]}

Yonamine, Tsunaki ^{[1
]}

Higashi, Masahiro ^{[1
]}

机构：

[1] Univ Ryukyus, Dept Chem Biol & Marine Sci, Senbaru 1, Nishihara, Okinawa 9030213, Japan

来源：

ACS CATALYSIS | 2017年 / 7卷 / 07期

关键词：

dienamine; organocatalysis; fluorinated quaternary carbon; allylic fluoride; CH hydrogen bond; VINYLOGOUS ALDOL REACTION; PHASE-TRANSFER CATALYSIS; ALPHA; BETA-UNSATURATED ALDEHYDES; GAMMA-ALKYLATION; DIRECTING GROUP; HYDROGEN-BOND; CH; BENZOYLOXYLATION; ORGANOCATALYSIS; ACTIVATION;

D O I：

10.1021/acscatal.7b01178

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Fluorination of dienamines generated by alpha-branched enals and 6'-hydroxy-9-amino-9-deoxy-epi-quinidine (30 mol %) with NSFI show excellent alpha-regioselectivity to construct allylic fluorides containing a highly stereocontrolled quaternary fluorinated carbon (E/Z >= 20/1 and up to 93% enantiometric excess (ee)). By DFT calculation, the quinuclidine moiety of the catalyst was shown to function as a coordinating group to promote a reaction at the proximal alpha-position, and the nonclassical CH hydrogen bond plays an important role in the high enantioselectivity.

引用

页码：4736 / 4740

页数：5

共 20 条

[1] Cinchona-based Primary Amine Catalysis in the Asymmetric Functionalization of Carbonyl Compounds
Melchiorre, Paolo
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2012, 51 (39) : 9748 - 9770
[2] Enantioselective Fluorination of α-Branched β-Ynone Esters Using a Cinchona-Based Phase-Transfer Catalyst
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[3] Improvement of primary-amine-catalyzed asymmetric α-benzoyloxylation of α-branched enals by a synergistic effect of water and sulfonic acids
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[4] Cinchona-based primary amine-catalyzed enantioselective aza-Michael reactions of pyrroles with α,β-unsaturated aldehydes
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Ahn, Jun-Gi
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[5] Secondary Amine-Catalyzed Asymmetric γ-Alkylation of α-Branched Enals via Dienamine Activation
Silvi, Mattia
Cassani, Carlo
Moran, Antonio
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[6] Enantioselective γ-Alkylation of α,β-Unsaturated Aldehydes Using New Cinchona-Based Primary Amine Catalyst
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[7] The development of asymmetric primary amine catalysts based on cinchona alkaloids
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SYNLETT, 2008, (13) : 1919 - 1930
[8] Asymmetric Fluorination of α-Branched Aldehydes by Chiral Primary Amine Catalysis: Reagent-Controlled Enantioselectivity Switch
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You, Yang'en
Mi, Xueling
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[9] The Cinchona Primary Amine-Catalyzed Asymmetric Epoxidation and Hydroperoxidation of α,β-Unsaturated Carbonyl Compounds with Hydrogen Peroxide
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Lee, Anna
Fares, Christophe
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List, Benjamin
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (17) : 6677 - 6693
[10] A semipinacol rearrangement of vinylogous α-ketol cocatalyzed by a cinchona-based primary amine andN-Boc-phenylglycines: mechanisms, roles of catalysts and the origin of enantioselectivity
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