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Phosphine‐Catalyzed Interrupted Morita–Baylis–Hillman Reaction and Switchable Domino Reactions of α‐Substituted Activated Olefins with Formaldehyde and Mechanism Elucidation
Author(s) -
Gu Jing,
Xiao BenXian,
Ouyang Qin,
Du Wei,
Chen YingChun
Publication year - 2019
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.201800466
Subject(s) - chemistry , aldol reaction , catalysis , ylide , cascade reaction , hydride , baylis–hillman reaction , formaldehyde , phosphine , domino , combinatorial chemistry , organic chemistry , medicinal chemistry , hydrogen
Summary of main observation and conclusion 3‐Olefinic oxindoles can undergo interrupted Morita‐Baylis‐Hillman reaction with formaldehyde. Apart from the previous reported dephosphoration to access reductive aldol‐type products, here we uncovered that completely different pathways were followed by tuning the substitutions of 3‐olefinic oxindoles. In combination with formalin, an unexpected domino phosphorus‐ylide formation, aldol‐type addition, hemeacetal formation and O‐substitution process was observed to produce 1,3‐dioxolane derivatives. Moreover, a switchable sequence to produce formate derivatives via a key hydride transfer process was furnished by simply replacing formalin with paraformaldehyde. Density functional theory calculations were conducted to well elucidate the catalytic reaction mechanism.