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Synlett 2023; 34(04): 314-326
DOI: 10.1055/s-0042-1751391
DOI: 10.1055/s-0042-1751391
account
Reductive Umpolung and Defunctionalization Reactions through Higher-Order Titanium(III) Catalysis
The Fonds der Chemischen Industrie (FCI) (Liebig Fellowship and Dozentenpreis) and the Deutsche Forschungsgemeinschaft (DFG) (Grants: 213717717, 275166688, 275167197, 240508776, 333382543, 408295365) are gratefully acknowledged for their long-standing support.
Abstract
The single-electron transfer from an in situ formed titanium(III) catalyst to ketones, imines, nitriles, Michael acceptors, and many other functions has enabled a large number of intra- and intermolecular reductive umpolung reactions. Likewise, it allows the homolytic cleavage of functional groups for selective defunctionalizations. These reactions often take place with the participation of two titanium(III) species, avoiding free-radical pathways and enabling high catalyst control of the reaction selectivity. This account discusses the development of the individual reactions together with the fundamental mechanistic discoveries that led to a better understanding of such titanium(III)-catalyzed processes in general.
1 Introduction
2 Active Titanium(III) Species and Additives
3 Ketone-Nitrile Couplings
4 Further Reductive Umpolung Reactions
5 Catalytic Homolytic C–CN and C–SO2R Cleavage
6 Conclusion
Publication History
Received: 13 October 2022
Accepted after revision: 04 November 2022
Article published online:
23 December 2022
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Selected work:
For important stoichiometric examples, see:
For examples, see:
For other syntheses, see:
See also:
Selected works:
Selected desulfonylation examples: