Asymmetric Iodoamination of Chalcones and 4-Aryl-4-oxobutenoates Catalyzed by a Complex Based on Scandium(III) and a N,N′-Dioxide Ligand

被引：79

作者：

Cai, Yunfei ^{[1
]}

Liu, Xiaohua ^{[1
]}

Li, Jun ^{[1
]}

Chen, Weiliang ^{[1
]}

Wang, Wentao ^{[1
]}

Lin, Lili ^{[1
]}

Feng, Xiaoming ^{[1
]}

机构：

[1] Sichuan Univ, Coll Chem, Minist Educ, Key Lab Green Chem & Technol, Chengdu 610064, Peoples R China

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2011年 / 17卷 / 52期

基金：

中国国家自然科学基金;

关键词：

asymmetric catalysis; dioxides; iodoamination; iodonium ions; scandium; STEREOSELECTIVE AMINOBROMINATION; AMINOHALOGENATION REACTION; ELECTROPHILIC DIAMINATION; NITROGEN; OLEFINS; ALKENES; TSNH2; NBS; AMINOCHLORINATION; CHLOROAMINATION;

D O I：

10.1002/chem.201102453

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Highly diastereo- and enantioselective iodoamination of chalcones, 4-aryl-4-oxobutenoates, and a trifluoro-substituted enone has been accomplished in the presence of a chiral N,N'-dioxide/[Sc(OTf)3] complex (0.52 mol%), delivering the desired vicinal anti-alpha-iodo-beta-amino carbonyl compounds regioselectively in high yields (up to 97%) and with excellent diastereoselectivities (>99:1 d.r.) and enantioselectivities (up to 99% ee). Enantiopure syn-alpha-iodo-beta-amino products could also be obtained from the isomerization of particular iodo compounds. TsNHX species (X=Cl, Br, I), generated from the reactions between the halo sources and TsNH2, were further confirmed as the active species in the haloamination reactions involved in the formation of the key halonium ion intermediates. A typical haloamination dependency was observed, with reactivity decreasing in the order NBS>NIS >> NCS.

引用

页码：14916 / 14921

页数：6

共 51 条

[1] BANERJI KK, 1987, J SCI IND RES INDIA, V46, P65
[2] Organocatalytic asymmetric α-bromination of aldehydes and ketones
Bertelsen, S
Halland, N
Bachmann, S
Marigo, M
Braunton, A
Jorgensen, KA
[J]. CHEMICAL COMMUNICATIONS, 2005, (38) : 4821 - 4823
[3] BLOCK SS, 2001, DISINFECTION STERILI, P160
[4] The generation and trapping of enantiopure bromonium ions
Braddock, D. Christopher
Hermitage, Stephen A.
Kwok, Lilian
Pouwer, Rebecca
Redmond, Joanna M.
White, Andrew J. P.
[J]. CHEMICAL COMMUNICATIONS, 2009, (09) : 1082 - 1084
[5] Investigation of the early steps in electrophilic bromination through the study of the reaction with sterically encumbered olefins
Brown, RS
[J]. ACCOUNTS OF CHEMICAL RESEARCH, 1997, 30 (03) : 131 - 137
[6] Cai Y., 2010, ANGEW CHEM, V122, P6296
[7] Catalytic Asymmetric Chloroamination Reaction of α,β-Unsaturated γ-Keto Esters and Chalcones
Cai, Yunfei
Liu, Xiaohua
Jiang, Jun
Chen, Weiliang
Lin, Lili
Feng, Xiaoming
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (15) : 5636 - 5639
[8] Catalytic Asymmetric Bromoamination of Chalcones: Highly Efficient Synthesis of Chiral α-Bromo-β-Amino Ketone Derivatives
Cai, Yunfei
Liu, Xiaohua
Hui, Yonghai
Jiang, Jun
Wang, Wentao
Chen, Weiliang
Lin, Lili
Feng, Xiaoming
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2010, 49 (35) : 6160 - 6164
[9] Current Methods for Asymmetric Halogenation of Olefins
Castellanos, Alejandro
Fletcher, Stephen P.
[J]. CHEMISTRY-A EUROPEAN JOURNAL, 2011, 17 (21) : 5766 - 5776
[10] Chen DJ, 2004, EUR J ORG CHEM, V2004, P3097

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