Ligand-Enabled Copper-Catalyzed Regio- and Stereoselective Allylboration of 1-Trifluoromethylalkenes

被引：6

作者：

Kojima, Yuki ^{[1
]}

Nishii, Yuji ^{[1
]}

Hirano, Koji ^{[1
,2
]}

机构：

[1] Osaka Univ, Grad Sch Engn, Dept Appl Chem, Suita, Osaka 5650871, Japan

[2] Osaka Univ, Inst Open & Transdisciplinary Res Initiat ICS OTRI, Innovat Catalysis Sci Div, Suita, Osaka 5650871, Japan

来源：

ORGANIC LETTERS | 2022年 / 24卷 / 40期

关键词：

BORYL COMPLEXES; BORONIC ESTERS; CU; TRIFLUOROMETHYLATION; CARBOBORATION; FLUORINE; CARBONYL; ALKYNES; SCOPE; DFT;

D O I：

10.1021/acs.orglett.2c03024

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A copper-catalyzed regio-and stereoselective allylboration of 1-trifluoromethylalkenes with bis(pinacolato)-diboron (pinB-Bpin) and allylic chlorides has been developed to form functionalized trifluoromethylated products with high diastereoselectivity. The key to success is the judicious choice of Cs2CO3 base and t-Bu-modified dppe-type ligand, which enables the otherwise challenging high catalyst turnover and suppression of the competing defluorination side reaction from an alkylcopper intermediate. The product derivatization of the resulting Bpin moiety can deliver diverse CF3-containing molecules with high stereochemical fidelity.

引用

页码：7450 / 7454

页数：5

共 39 条

[1] Copper(I)-Catalyzed Formal Carboboration of Alkynes: Synthesis of Tri- and Tetrasubstituted Vinylboronates
Alfaro, Ricardo
Parra, Alejandro
Aleman, Jose
Garcia Ruano, Jose Luis
Tortosa, Mariola
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (37) : 15165 - 15168
[2] Carbon Trifluoromethylation Reactions of Hydrocarbon Derivatives and Heteroarenes
Alonso, Concepcion
Martinez de Marigorta, Eduardo
Rubiales, Gloria
Palacios, Francisco
[J]. CHEMICAL REVIEWS, 2015, 115 (04) : 1847 - 1935
[3] Bonet A, 2014, NAT CHEM, V6, P584, DOI [10.1038/NCHEM.1971, 10.1038/nchem.1971]
[4] Elusive Phosphine Copper(l) Boryl Complexes: Synthesis, Structures, and Reactivity
Borner, Corinna
Anders, Lisa
Brandhorst, Kai
Kleeberg, Christian
[J]. ORGANOMETALLICS, 2017, 36 (24) : 4687 - 4690
[5] DFT studies on the borylation of α,β-unsaturated carbonyl compounds catalyzed by phosphine copper(I) boryl complexes and observations on the interconversions between O- and C-bound enolates of Cu, B, and Si
Dang, Li
Lin, Zhenyang
Marder, Todd B.
[J]. ORGANOMETALLICS, 2008, 27 (17) : 4443 - 4454
[6] DFT studies of alkene insertions into Cu-B bonds in copper(I) boryl complexes
Dang, Li
Zhao, Haitao
Lin, Zhenyang
Marder, Todd B.
[J]. ORGANOMETALLICS, 2007, 26 (11) : 2824 - 2832
[7] Catalytic Asymmetric Hydrogenation of α-CF3- or β-CF3-Substituted Acrylic Acids using Rhodium(I) Complexes with a Combination of Chiral and Achiral Ligands
Dong, Kaiwu
Li, Yang
Wang, Zheng
Ding, Kuiling
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2013, 52 (52) : 14191 - 14195
[8] Applications of Fluorine in Medicinal Chemistry
Gillis, Eric P.
Eastman, Kyle J.
Hill, Matthew D.
Donnelly, David J.
Meanwell, Nicholas A.
[J]. JOURNAL OF MEDICINAL CHEMISTRY, 2015, 58 (21) : 8315 - 8359
[9] Catalytic Asymmetric Construction of CF3-Substituted Chiral sp3 Carbon Centers
Hirano, Koji
[J]. SYNTHESIS-STUTTGART, 2022, 54 (17): : 3708 - 3718
[10] Contribution of Organofluorine Compounds to Pharmaceuticals
Inoue, Munenori
Sumii, Yuji
Shibata, Norio
[J]. ACS OMEGA, 2020, 5 (19): : 10633 - 10640

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