Catalytic asymmetric synthesis of a nitrogen heterocycle through stereocontrolled direct photoreaction from electronically excited state

Xiaoqiang Huang, Xinyao Li, Xiulan Xie, Klaus Harms, Radostan Riedel and Eric Meggers ()
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Xiaoqiang Huang: Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4
Xinyao Li: State Key Laboratory of Natural and Biomimetic Drugs, Peking University
Xiulan Xie: Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4
Klaus Harms: Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4
Radostan Riedel: Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4
Eric Meggers: Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4

Nature Communications, 2017, vol. 8, issue 1, 1-8

Abstract: Abstract The reactivity of photoexcited molecules has been extensively studied for decades but until today direct bond-forming reactions of such excited states in a catalytic and asymmetric fashion are restricted to the synthesis of cyclobutanes via [2 + 2] photocycloadditions. Herein, we demonstrate a previously elusive visible-light-induced catalytic asymmetric [2 + 3] photocycloaddition of alkenes with vinyl azides. A wide range of complex 1-pyrrolines are obtained as single diastereoisomers and with up to >99% enantiomeric excess using a simple reaction setup and mild reaction conditions. The reaction is proposed to proceed through the photoexcitation of a complex out of chiral rhodium catalyst coordinated to α,β-unsaturated N-acylpyrazole substrates. All reactive intermediates remain bound to the catalysts thereby providing a robust catalytic scheme (no exclusion of air necessary) with excellent stereocontrol. This work expands the scope of stereocontrolled bond-forming reactions of photoexcited intermediates by providing catalytic asymmetric access to a key nitrogen heterocycle in organic chemistry.

Date: 2017
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DOI: 10.1038/s41467-017-02148-1

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