Catalytic activations of unstrained C–C bond involving organometallic intermediates

Abstract

The cleavage of C-C bonds has been a great challenge owing to their thermodynamic and kinetic stability. To date, the progress made in this area has mainly relied on the reaction of small rings, which is driven by releasing ring strain. Encouragingly, more and more examples of the cleavage of non-strained C-C bonds have been reported. This review provides a comprehensive overview of the transition-metal-catalyzed C-C bond activation of relatively stable and unstrained molecules that involves the formation of organometallic intermediates. In the first section we focus on the C-C bond activation achieved through β-carbon elimination, and in the second section the oxidative addition of the C-C bond to low-valent metal is summarized in detail.

Direct C2‐Heteroarylation of Indoles by Rhodium‐Catalyzed C−C Bond Cleavage of Secondary Alcohols

“…However, transition‐metal catalyzed C−C bond cleavage is challenging. For example, C−C bond activation of secondary alcohols faces two challenges: (i) β‐H elimination of metal‐alcoholate is often preferred over β‐C elimination owing to higher stability of M−H bond, which makes C−C bond cleavage thermodynamically disfavored; (ii) secondary alcohols could be easily converted to ketones under oxidative conditions (Scheme ) . Despite the challenges of this field, various significant studies have been reported, such as those by Shi, Kang, Yin and Morandi .…”

Recent Advances in the Synthesis of Sulfides, Sulfoxides and Sulfones via C-S Bond Construction from Non-Halide Substrates

“…A great variety of N-tosylhydrazones and disulfides were successfully converted into the corresponding dithioacetals in moderate to good yields. C−C bond fragmentation is a useful method to provide a fragment for the functionalization of molecules and has been extensively applied in organic synthesis [19]. In recent years, C-C bond cleavage/sulfenylation reactions via radical pathways have emerged as a practical tool for the synthesis of aryl alkyl sulfides [20].…”

Nickel(0)‐Catalyzed Enantioselective [3+2] Annulation of Cyclopropenones and α,β‐Unsaturated Ketones/Imines

“…Inthe past decade,c atalytic CÀCb ond activation has received increasing attention, allowing facile reconstruction and reorganization of carbon skeletons. [1] TheC À Cb ond activation is typically fulfilled through two elementary,n onradical reaction pathways,namely the CÀCoxidative addition and b-carbon elimination. [1] Despite the advancement, the majority of reported systems rely on noble metal catalysis.…”

“…[1] TheC À Cb ond activation is typically fulfilled through two elementary,n onradical reaction pathways,namely the CÀCoxidative addition and b-carbon elimination. [1] Despite the advancement, the majority of reported systems rely on noble metal catalysis. [2][3][4] In addition, the development of asymmetric catalytic C À C bond activation systems severely lags behind, [5,6] even for activated C À Cb onds,a nd previously reported systems are predominantly initiated by chelation-assisted CÀCb ond oxidative addition, followed by intramolecular insertion into aC =C, C=O, or C=Nbond (Schemes 1a).…”