Enantioselective Cu(I)-catalyzed borylative cyclization of enone-tethered cyclohexadienones and mechanistic insights

Sandip B. Jadhav, Soumya Ranjan Dash, Sundaram Maurya, Jagadeesh Babu Nanubolu, Kumar Vanka and Rambabu Chegondi ()
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Sandip B. Jadhav: CSIR-Indian Institute of Chemical Technology (CSIR-IICT)
Soumya Ranjan Dash: Academy of Scientific and Innovative Research (AcSIR)
Sundaram Maurya: CSIR-Indian Institute of Chemical Technology (CSIR-IICT)
Jagadeesh Babu Nanubolu: Academy of Scientific and Innovative Research (AcSIR)
Kumar Vanka: Academy of Scientific and Innovative Research (AcSIR)
Rambabu Chegondi: CSIR-Indian Institute of Chemical Technology (CSIR-IICT)

Nature Communications, 2022, vol. 13, issue 1, 1-11

Abstract: Abstract The catalytic asymmetric borylation of conjugated carbonyls followed by stereoselective intramolecular cascade cyclizations with in situ generated chiral enolates are extremely rare. Herein, we report the enantioselective Cu(I)-catalyzed β-borylation/Michael addition on prochiral enone-tethered 2,5-cyclohexadienones. This asymmetric desymmetrization strategy has a broad range of substrate scope to generate densely functionalized bicyclic enones bearing four contiguous stereocenters with excellent yield, enantioselectivity, and diastereoselectivity. One-pot borylation/cyclization/oxidation via the sequential addition of sodium perborate reagent affords the corresponding alcohols without affecting yield and enantioselectivity. The synthetic potential of this reaction is explored through gram-scale reactions and further chemoselective transformations on products. DFT calculations explain the requirement of the base in an equimolar ratio in the reaction, as it leads to the formation of a lithium-enolate complex to undergo C-C bond formation via a chair-like transition state, with a barrier that is 22.5 kcal/mol more favourable than that of the copper-enolate complex.

Date: 2022
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DOI: 10.1038/s41467-022-28288-7

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