Carboboration of Alkynes with Cyclodextrin-Encapsulated N-Heterocyclic Carbene Copper Complexes

被引:18
作者
Wen, Zhonghang [1 ]
Zhang, Yongmin [1 ]
Roland, Sylvain [1 ]
Sollogoub, Matthieu [1 ]
机构
[1] Sorbonne Univ, CNRS, UMR 8232, Inst Parisien Chim Mol, Campus P & M Curie 4,Pl Jussieu, F-75005 Paris, France
关键词
Catalysis; Copper; Cyclodextrins; Regioselectivity; Supramolecular chemistry; DEHYDROGENATIVE BORYLATION; CATALYZED BORYLATION; ALKYLBORATION; ALKENES; REGIOSELECTIVITY; ISOMERIZATION; CYCLIZATION; HALIDES;
D O I
10.1002/ejoc.201900246
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The copper-catalyzed carboboration of various alkynes was investigated with a modified N-heterocyclic carbene-capped alpha-cyclodextrin copper(I) complex in which the reactive copper center is deeply encapsulated in the cyclodextrin (CD) cavity. The methylborylation of terminal alkynes was found to give linear (L) (E)-vinyl boron isomers as the major isomers, as expected from the previously proposed "perpendicular" approach of the alkyne to the Cu-B bond, and methylation of the vinyl boron copper intermediate. Under similar conditions, the intramolecular carboboration reaction with terminal alkynes functionalized by alkyl halides, led to exocyclic vinyl boronate species as the major isomer. However, an endocyclic (Z)-isomer was also observed in some cases. This isomer was not previously observed and is unexpected considering the "classical" mechanism. The direct generation of boron functionalized (Z)-alkenes by carboboration of alkynes is unprecedented.
引用
收藏
页码:2682 / 2687
页数:6
相关论文
共 50 条
[41]   Fluorinated N-Heterocyclic carbene complexes. Applications in catalysis [J].
Rufino-Felipe, Ernesto ;
Valdes, Hugo ;
Manuel German-Acacio, Juan ;
Reyes-Marquez, Viviana ;
Morales-Morales, David .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2020, 921
[42]   A direct and practical approach for the synthesis of N-heterocyclic carbene coinage metal complexes [J].
Zhu, Shifa ;
Liang, Renxiao ;
Jiang, Huanfeng .
TETRAHEDRON, 2012, 68 (38) :7949-7955
[43]   Synthesis and catalytic application of cyclopentadienyl nickel(II) N-heterocyclic carbene complexes [J].
Demir Atli, Deniz .
JOURNAL OF COORDINATION CHEMISTRY, 2020, 73 (10) :1530-1537
[44]   Rhodium(I) N-Heterocyclic Carbene Complexes as Catalysts for Hydroformylation of Olefins: An Overview [J].
Almeida, Ana R. ;
Peixoto, Andreia F. ;
Calvete, Mario J. F. ;
Gois, Pedro M. P. ;
Pereira, Mariette M. .
CURRENT ORGANIC SYNTHESIS, 2011, 8 (05) :764-775
[45]   (N-Heterocyclic Carbene)2-Pd(0)-Catalyzed Silaboration of Internal and Terminal Alkynes: Scope and Mechanistic Studies [J].
Ansell, Melvyn B. ;
Spencer, John ;
Navarro, Oscar .
ACS CATALYSIS, 2016, 6 (04) :2192-2196
[46]   Aerobic synthesis of N-sulfonylamidines mediated by N-heterocyclic carbene copper(I) catalysts [J].
Lazreg, Falima ;
Vasseur, Marie ;
Slawin, Alexandra M. Z. ;
Cazin, Catherine S. J. .
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY, 2020, 16 :482-491
[47]   N-donor functionalized N-heterocyclic carbene nickel(II) complexes in the Kumada coupling [J].
Berding, Joris ;
van Dijkman, Thomas F. ;
Lutz, Martin ;
Spek, Anthony L. ;
Bouwman, Elisabeth .
DALTON TRANSACTIONS, 2009, (35) :6948-6955
[48]   Synthesis of Cationic N-Heterocyclic Carbene Lanthanide Bromide and the Influence of N-Heterocyclic Carbene and Lanthanide Metals [J].
Yao, Haisheng ;
Zhang, Jinguo ;
Zhang, Yong ;
Sun, Hongmei ;
Shen, Qi .
ORGANOMETALLICS, 2010, 29 (22) :5841-5846
[49]   N-Heterocyclic carbene copper-catalyzed direct alkylation of terminal alkynes with non-activated alkyl triflates [J].
Jin, Liqun ;
Hao, Wangfang ;
Xu, Jianeng ;
Sun, Nan ;
Hu, Baoxiang ;
Shen, Zhenlu ;
Mo, Weimin ;
Hu, Xinquan .
CHEMICAL COMMUNICATIONS, 2017, 53 (29) :4124-4127
[50]   N-Heterocyclic Carbene Boryl Iodides Catalyze Insertion Reactions of N-Heterocyclic Carbene Boranes and Diazoesters [J].
Allen, Thomas H. ;
Kawamoto, Takuji ;
Gardner, Sean ;
Geib, Steven J. ;
Curran, Dennis P. .
ORGANIC LETTERS, 2017, 19 (13) :3680-3683