Enantioselective Alkynylation of Trifluoromethyl Ketones Catalyzed by Cation-Binding Salen Nickel Complexes

被引：33

作者：

Park, Dongseong ^{[1
]}

Jette, Carina, I ^{[2
]}

Kim, Jiyun ^{[1
]}

Jung, Woo-Ok ^{[1
]}

Lee, Yongmin ^{[3
]}

Park, Jongwoo ^{[4
,5
]}

Kang, Seungyoon ^{[1
]}

Han, Min Su ^{[1
]}

Stoltz, Brian M. ^{[2
]}

Hong, Sukwon ^{[1
,3
]}

机构：

[1] GIST, Dept Chem, 123 Cheomdan Gwagiro, Gwangju 61005, South Korea

[2] CALTECH, Warren & Katharine Schlinger Lab Chem & Chem Engn, Pasadena, CA 91125 USA

[3] GIST, Sch Mat Sci & Engn, 123 Cheomdan Gwagiro, Gwangju 61005, South Korea

[4] Univ Florida, Dept Chem, POB 117200, Gainesville, FL 32611 USA

[5] SK Biotek 325 Exporo, Proc R&D Ctr, Daejeon 34124, South Korea

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2020年 / 59卷 / 02期

基金：

美国国家科学基金会; 新加坡国家研究基金会;

关键词：

alkynylation; bifunctional catalysis; nickel; trifluoromethylketones; ASYMMETRIC ALKYNYLATION; RHODIUM(III) COMPLEXES; KINETIC RESOLUTION; AROMATIC-ALDEHYDES; PHENYLACETYLENE; ACCESS; LIGAND; SITE;

D O I：

10.1002/anie.201913057

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Cation-binding salen nickel catalysts were developed for the enantioselective alkynylation of trifluoromethyl ketones in high yield (up to 99 %) and high enantioselectivity (up to 97 % ee). The reaction proceeds with substoichiometric quantities of base (10-20 mol % KOt-Bu) and open to air. In the case of trifluoromethyl vinyl ketones, excellent chemo-selectivity was observed, generating 1,2-addition products exclusively over 1,4-addition products. UV-vis analysis revealed the pendant oligo-ether group of the catalyst strongly binds to the potassium cation (K+) with 1:1 binding stoichiometry (K-a=6.6x10(5) m(-1)).

引用

页码：775 / 779

页数：5

共 50 条

[1] Enantioselective alkynylation of trifluoromethyl ketones catalyzed by functionalized-salen Ni complexes
Hong, Sukwon
Park, Minsung
Kim, Jiyun
Lee, Yongmin
Park, Jongwoo
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2014, 248
[2] Enantioselective alkynylation of ketones catalyzed by Zn(salen) complexes
Cozzi, PG
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2003, 42 (25) : 2895 - 2898
[3] Enantioselective Alkynylation of Trifluoromethyl Ketones Catalyzed by Chiral Schiff Bases
Dhayalan, Vasudevan
Murakami, Ryo
Hayashi, Masahiko
ASIAN JOURNAL OF CHEMISTRY, 2013, 25 (13) : 7505 - 7508
[4] Zn(salen)-catalyzed asymmetric alkynylation of ketones
Saito, B
Katsuki, T
SYNLETT, 2004, (09) : 1557 - 1560
[5] Enantioselective Direct Alkynylation of Ketones Catalyzed by Chiral CCN Pincer RhIII Complexes
Ito, Jun-ichi
Ubukata, Shino
Muraoka, Shun
Nishiyama, Hisao
CHEMISTRY-A EUROPEAN JOURNAL, 2016, 22 (47) : 16800 - 16803
[6] Copper(I) alkoxide-catalyzed alkynylation of trifluoromethyl ketones
Motoki, Rie
Kanai, Motomu
Shibasaki, Masakatsu
ORGANIC LETTERS, 2007, 9 (16) : 2997 - 3000
[7] Kinetic Resolution of β-Sulfonyl Ketones through Enantioselective β-Elimination using a Cation-Binding Polyether Catalyst
Li, Liang
Liu, Yidong
Peng, Yang
Yu, Lei
Wu, Xiaoyan
Yan, Hailong
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (01) : 331 - 335
[8] Enantioselective alkynylation of aromatic ketones catalyzed by chiral camphorsulfonamide ligands
Lu, G
Li, XS
Jia, X
Chan, WL
Chan, ASC
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2003, 42 (41) : 5057 - 5058
[9] Enantioselective rhodium(I)-catalyzed hydrogenation of trifluoromethyl ketones
Kuroki, Y
Sakamaki, Y
Iseki, K
ORGANIC LETTERS, 2001, 3 (03) : 457 - 459
[10] Sulfamide-amine alcohol catalyzed enantioselective alkynylation of aromatic ketones
Mao, JC
Wan, BS
Wu, F
Lu, SW
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2005, 237 (1-2) : 126 - 131

← 1 2 3 4 5 →