Formal Alkylation of Allenes through Highly Selective Radical Cyclizations of Allene‐enes

Zeng, Rong; Fu, Chunling; Ma, Shengming

doi:10.1002/ange.201107747

Cited by 5 publications

(1 citation statement)

References 42 publications

(7 reference statements)

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“…402 In 2012, Ma and co-workers developed a Zn-catalyzed radical addition of perfluoroalkyl iodides to enallenes 347, affording cyclic vinyl iodides 348 in moderate to good yields (Scheme 232). 403 Contrary to the traditional "allene-to-alkene" radical cyclization mode, 404,405 an "alkene-to-allene" cyclization mode was observed. In other terms, the perfluoroalkyl radical first adds to the alkene to generate radical intermediate 349, which undergoes 5-exo cyclization to generate vinyl radical 350.…”

Section: Radical Reactionsmentioning

confidence: 47%

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

2016

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The high utility of halogenated organic compounds has prompted the development of a vast number of transformations which install the carbon-halogen motif. Traditional routes to these building blocks have commonly involved multiple steps, harsh reaction conditions, and the use of stoichiometric and/or toxic reagents. In this regard, using transition metals to catalyze the synthesis of organohalides has become a mature field in itself, and applying these technologies has allowed for a decrease in the production of waste, higher levels of regio- and stereoselectivity, and the ability to produce enantioenriched target compounds. Furthermore, transition metals offer the distinct advantage of possessing a diverse spectrum of mechanistic possibilities which translate to the capability to apply new substrate classes and afford novel and difficult-to-access structures. This Review provides comprehensive coverage of modern transition metal-catalyzed syntheses of organohalides via a diverse array of mechanisms. Attention is given to the seminal stoichiometric organometallic studies which led to the corresponding catalytic processes being realized. By breaking this field down into the synthesis of aryl, vinyl, and alkyl halides, it becomes clear which methods have surfaced as most favored for each individual class. In general, a pronounced shift toward the use of C-H bonds as key functional groups, in addition to methods which proceed by catalytic, radical-based mechanisms has occurred. Although always evolving, this field appears to be heading in the direction of using starting materials with a significantly lower degree of prefunctionalization in addition to less expensive and abundant metal catalysts.

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Section: Radical Reactionsmentioning

confidence: 47%

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

2016

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Iron‐Catalyzed 1,2‐Addition of Perfluoroalkyl Iodides to Alkynes and Alkenes

Cheung

2014

Angewandte Chemie

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Iron catalysis has been developed for the intermolecular 1,2‐addition of perfluoroalkyl iodides to alkynes and alkenes. The catalysis has a wide substrate scope and high functional‐group tolerance. A variety of perfluoroalkyl iodides including CF3I can be employed. The resulting perfluoroalkylated alkyl and alkenyl iodides can be further functionalized by cross‐coupling reactions. This methodology provides a straightforward and streamlined access to perfluoroalkylated organic molecules.

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