Rhodium-Catalyzed β-Acylalkylation of Allylbenzene Derivatives with Allyl Alcohols via C–C Bond Cleavage

Ishikawa, Soya; Togashi, Ryo; Ueda, Ryosuke; Onodera, Shunsuke; Kochi, Takuya; Kakiuchi, Fumitoshi

doi:10.1021/acs.joc.2c02776

Cited by 3 publications

(1 citation statement)

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“…In recent years, several elegant examples have been reported that addressed these issues to some extent. For example, chelation-assisted functionalizations of allylbenzenes have been achieved via the activation of nonpolar C–C bonds . Our group achieved a Ag-catalyzed 1,4-aryl migration of γ,γ-disubstituted triflic amides from carbon to the nitrogen center, which cleaved the C–C bond far from the polar group through a radical pathway .…”

Section: Discussionmentioning

confidence: 99%

Transition-Metal-Catalyzed C–C Bond Formation from C–C Activation

Song,

Wang,

Shi

2023

Acc. Chem. Res.

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Ni-catalyzed cross coupling of aryl nitriles with arylboronic esters through C−CN cleavage. Encouraged by these results, we are interested in transition-metal-catalyzed C−C bond activation. Due to their broad availability, we then turned our attention to C−C cleavage of carboxylic acids. Rhodiumcatalyzed decarbonylative coupling of carboxylic acids with (hetero)arenes was then achieved through oxidative addition of in situ formed, more reactive mixed anhydrides to Rh(I) without the need for oxidants that are commonly required for the decarboxylative coupling of carboxylic acids. Subsequently, the decarbonylation of more challenging unstrained aryl ketones was realized under Rh catalysis assisted by N-containing directing groups. Following this work, a group exchange of aryl ketones with carboxylic acids was achieved through 2-fold C−C bond cleavage. By employing the chelation strategy, Rh-catalyzed C−C bond activation of secondary benzyl alcohols was also accomplished through β-carbon elimination of the rhodium alcoholate intermediates. The competing oxidation of secondary alcohols to ketones via β-hydrogen elimination of the same intermediates was suppressed as thermodynamically favorable five-membered rhodacycles are formed after β-carbon elimination. Different types of transformations of alcohols, including the Heck-type reaction with alkenes, cross coupling with arylsilanes, and Grignard-type addition with aldehydes or imines, have been achieved, showing the great potential of secondary alcohols in the formation of C−C bonds. These C−C bond-forming reactions are complementary to traditional cross couplings of aryl halides with organometallic reagents. However, these transformations produce small molecules as byproducts. To improve the atom economy, we then investigated C−C bond transformations of strained-ring cyclic compounds. Ni-catalyzed intermolecular cyclization of benzocyclobutenones with alkynes was recently achieved via the uncommon cleavage of the C1−C8 bond by employing a removable blocking strategy. Rhcatalyzed intramolecular annulation of benzocyclobutenols with alkynes was also achieved. In summary, our developments demonstrate the great potential of transition-metal-catalyzed C−C bond activation for the formation of new C−C bonds. To further expand the synthetic utility of C−C bond activation, more efforts are required to expand the substrate scope and to achieve earthabundant metal-catalyzed transformations.

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Section: Discussionmentioning

confidence: 99%