Spin-Selectivity in Photochemistry: A Tool for Organic Synthesis

Axel G. Griesbeck

doi:10.1055/s-2003-37505

ACCOUNT

Spin-Selectivity in Photochemistry: A Tool for Organic Synthesis

Axel G. Griesbeck*
University of Cologne, Institute of Organic Chemistry, Greinstr. 4, 50939 Köln, Germany
Fax: +49(221)4705057; e-Mail: griesbeck@uni-koeln.de;

Abstract

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Abstract

The photochemistry of carbonyl substrates is largely dependent on the spin multiplicity of the excited state. Singlet and triplet excited carbonyls can differ strongly in chemo-, regio- and stereoselectivity. In bimolecular Paternò-Büchi reactions, both excited singlet and triplets states give rise to oxetane formation, albeit with different selectivities and completely different activation parameters. In unimolecular photocyclizations (Norrish-Yang reaction) the triplet state dominates the reaction. For triplet to singlet intersystem crossing at the biradical level, spin-orbit coupling optimizing geometries are crucial. These geometries are different from classical closed-shell interactions and thus give rise to unusual product stereochemistry as well as unusual concentration and temperature dependences.

1 Introduction
2 The Carbonyl-Ene Photocycloaddition
2.1 First Surprises
2.2. First Concepts
2.3 Further Surprises
2.4 Further Concepts and Examples
2.5 Concentration and Temperature Studies
3 The Enone-Ene Photocycloaddition
4 The Norrish-Yang Photocyclization
4.1 The Classical Version
4.2 Extended Versions
4.3 Chirality Transfer and Memory of Chirality
5 Where to go?

Key words

photochemistry - biradicals - 90 rule - spin-orbit coupling geometries - photocycloaddition - photocyclization

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Referenzen

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