Pd-catalyzed Asymmetric Annulative Dearomatization of Phenols for Regio- and Enantioselective Synthesis of Spirocyclohexadienones

Hui-Lin Mao, Yu-Xin Wang, Xue Wang, Hai-Ying Wang,* Wen-Juan Hao,* Bo Jiang*

A palladium-catalyzed asymmetric annulative dearomatization of phenols with butene dicarbonate is reported, enabling twofold decarboxylative allylation to regioselectively produce a range of spirocyclohexadienones with 29–95% yields and 74–99% ee. A catalytic dearomative formal [4 + 2] cyclization of 1,1’-biphenyl-2,4’-diols delivered spiro[chromane-4,1'-cyclohexane]-2',5'-dien-4'-ones with high enantioselectivity, whereas enantioenriched spiro[cyclohexane-1,4'-quinoline]-2,5-dien-4-ones were generated starting from 2'-amino-[1,1'-biphenyl]-4-ols as 1,4-dinucleophiles.

Org. Lett. 2023, 25, 5963-5968; DOI: 10.1021/acs.orglett.3c02051