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Palladium‐Catalyzed Aerobic Synthesis of Terminal Acetals from Vinylarenes Assisted by π‐Acceptor Ligands
Author(s) -
Matsumura Satoko,
Sato Ruriko,
Nakaoka Sonoe,
Yokotani Wakana,
Murakami Yuka,
Kataoka Yasutaka,
Ura Yasuyuki
Publication year - 2017
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201601517
Subject(s) - chemistry , nucleophile , catalysis , markovnikov's rule , dissociation (chemistry) , palladium , acceptor , medicinal chemistry , ligand (biochemistry) , benzoquinone , combinatorial chemistry , photochemistry , polymer chemistry , organic chemistry , regioselectivity , physics , condensed matter physics , receptor , biochemistry
Terminal acetals were synthesized from various vinylarenes and 1,2‐ or 1,3‐diols using a simple PdCl 2 (MeCN) 2 /methoxy‐ p ‐benzoquinone (MeOBQ)/CuCl catalyst system and 1 atm of O 2 under mild reaction conditions by the anti‐Markovnikov nucleophilic attack of an oxygen nucleophile on the coordinated vinylarenes. Cyclic α,β‐unsaturated carbonyl compounds such as MeOBQ and N ‐phenylmaleimide were especially effective as additives to afford higher yields of the desired terminal acetals. Kinetic experiments indicated that MeOBQ operates as a π‐acceptor ligand for Pd to accelerate the reaction and that the dissociation of a chloride ion from Pd precedes the rate‐determining step.