Evidence for Triplet Sensitization in the Visible-Light-Induced [2+2] Photocycloaddition of Eniminium Ions

被引：74

作者：

Hoermann, Fabian M. ^{[1
,2
]}

Chung, Tim S. ^{[1
,2
]}

Rodriguez, Elsa ^{[1
,2
]}

Jakob, Matthias ^{[1
,2
]}

Bach, Thorsten ^{[1
,2
]}

机构：

[1] Tech Univ Munich, Dept Chem, Lichtenbergstr 4, D-85747 Garching, Germany

[2] Tech Univ Munich, CRC, Lichtenbergstr 4, D-85747 Garching, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2018年 / 57卷 / 03期

基金：

欧洲研究理事会;

关键词：

cycloaddition; enantioselectivity; enones; homogenous catalysis; photochemistry; IMINIUM SALTS; ENONE-OLEFIN; PHOTOCHEMISTRY; CATALYSIS; PHOTOCATALYSIS; CYCLOADDITIONS; COMPLEXES; POTENTIALS; MECHANISMS; CATION;

D O I：

10.1002/anie.201710441

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Eniminium ions were prepared from the corresponding alpha, beta-unsaturated carbonyl compounds (enones and enals), and were found to be promoted to their respective triplet states by energy transfer. The photoexcited intermediates underwent intra-or intermolecular [2+2] photocycloaddition in good yields (50-78%) upon irradiation at lambda = 433 nm or lambda = 457 nm. Iridium or ruthenium complexes with a sufficiently high triplet energy were identified as efficient catalysts (2.5 mol% catalyst loading) for the reaction. The intermolecular [2+2] photocycloaddition of an eniminium ion derived from a chiral secondary amine proceeded with high enantio-selectivity (88% ee).

引用

页码：827 / 831

页数：5

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