Cleavage of the Carbon—Carbon Bond in Biphenylene Using Transition Metals

Abstract

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Carbon–Carbon Bond Activation by Group 9 Metal Complexes

“…Table , Table and Table show the BDEs of M–C, H‐C and C–C bonds using alkyl or aryl complexes of cobalt, rhodium and iridium as the examples, respectively. This trend implies that the oxidative addition with a stronger C–C bond can be thermodynamically more favorable than the activation of a weaker C–C bond, given the compensation by forming two stronger M–C bonds in the organometallic product in the former case . However, the decrease in M–C bond strength with the hydrocarbyl group is more subtle than the decrease in the corresponding C–H and C–C bond strengths.…”

Rhodium(i)-catalyzed asymmetric [4 + 2] cycloaddition reactions of 2-alkylenecyclobutanols with cyclic enones through C–C bond cleavage: efficient access totrans-bicyclic compounds

“…Studies of transition-metal-catalyzed selective cleavage of carbon–carbon single bonds as the initiation for further functionalizations have grown considerably in recent years due to the high potential of this strategy in synthesis. 6 Cyclobutenols and cyclobutanols are privileged building blocks in this field. 7 Murakami pioneered a series of studies on the rhodium-catalyzed tandem C–C single bond cleavage/formal cycloaddition of benzocyclobutenols with various functionalities including alkynes, 7e , q vinyl ketones, 7 j carbene precursors, 7 l and allenes.…”

Rhodium(i)-catalyzed stereoselective [4+2] cycloaddition of oxetanols with alkynes through C(sp3)–C(sp3) bond cleavage

“…3 Among those, cyclobutanols are frequently employed as privileged building blocks for the construction of complex cyclic molecules. 4 In 2012, Murakami and co-workers reported seminal work on rhodium-catalyzed tandem C–C single bond cleavage/formal cycloaddition of benzocyclobutanols with alkynes [eqn (1)].…”