Selective alkane C-H‐bond functionalizations utilizing oxidative single‐electron transfer and organocatalysis
- 29 January 2004
- journal article
- research article
- Published by Wiley in The Chemical Record
- Vol. 3 (5) , 247-257
- https://doi.org/10.1002/tcr.10070
Abstract
Alkane CH‐bond functionalization methods not utilizing metal‐catalysis are discussed based on experimental and computational data, beginning with molecule‐induced homolysis (reactions of alkanes with dioxiranes). Electrophilic reactions are elaborated next with an emphasis on mechanistic details that reveal that many so‐called electrophilic CH or CC‐bond insertions can be rationalized by electron‐transfer reactions (inner sphere, H‐coupled, and outer sphere). Finally, radical functionalizations utilizing carbon‐centered (relatively stable) radicals generated under organocatalytic (phase‐transfer catalysis, PTC) conditions are presented as valuable alternatives to other radical‐chain alkane functionalizations. The remarkable chemo‐ and regioselectivities of these PTC radical reactions and the tolerance of high strain in certain aliphatic hydrocarbons make them particularly useful for laboratory‐scale halogenations, in particular, iodinations of unactivated alkane CH‐bonds. © 2004 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 3: 247–257; 2004: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.10070Keywords
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