期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 59, 期 51, 页码 23020-23024出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202009704
关键词
density functional calculations; energy transfer; homogeneous catalysis; photochemistry; visible light
资金
- EPSRC [EP/R005826/1]
- EPSRC via the Centre for Doctoral Training in Synthesis for Biology and Medicine [EP/ L015838/1]
- EPSRC [EP/R005826/1] Funding Source: UKRI
The [2+2] photocycloaddition is the most valuable and intensively investigated photochemical process. Here we demonstrate that irradiation of N-acryloyl heterocycles with blue LED light (440 nm) in the presence of an Ir(III)complex leads to efficient and high yielding fused gamma-lactam formation across a range of substituted heterocycles. Quantum calculations show that the reaction proceeds via cyclization in the triplet excited state to yield a 1,4-diradical; intersystem crossing leads preferentially to the closed shell singlet zwitterion. This is geometrically restricted from undergoing recombination to yield a cyclobutane by the planarity of the amide substituent. A prototropic shift leads to the observed bicyclic products in what can be viewed as an interrupted [2+2] cycloaddition.
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