Different Reaction Patterns in the Baylis-Hillman Reaction of Aryl Aldehydes with Phenyl Vinyl Ketone, Phenyl Acrylate and Phenyl Thioacrylate.docVIP

Molecules 2002, 7, 721-733 molecules ISSN 1420-3049 Different Reaction Patterns in the Baylis-Hillman Reaction of Aryl Aldehydes with Phenyl Vinyl Ketone, Phenyl Acrylate and Phenyl Thioacrylate Min Shi*, Chao-Qun Li and Jian-Kang Jiang State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032 China, Fax: (+86)-21* Author to whom correspondence should be addressed; e-mail: mshi@ Received: 27 August 2002; in revised form: 10 October 2002 / Accepted: 11 October 2002 / Published: 31 October 2002 Abstract: In the Baylis-Hillman reaction of aryl aldehydes with phenyl vinyl ketone we have observed exclusive formation of diadducts 4, and that the yields of diadduct can reach 80% with increasing amounts of phenyl vinyl ketone. On the other hand, for phenyl acrylate and phenyl thioacrylate, only the normal Baylis-Hillman adduct was obtained. The effects of substituents were also examined and a plausible reaction mechanism is proposed for the formation of compounds 4. Keywords: Baylis-Hillman reaction; Lewis base; Phenyl vinyl ketone (PVK); Phenyl acrylate; DABCO; Conjugate addition; DMAP. Introduction Great progress has been made in the implementation of the Baylis-Hillman reaction [1], since Baylis and Hillman first reported in 1972 the reaction of acetaldehyde with ethyl acrylate and acrylonitrile in the presence of catalytic amounts of 1,4-diazabicyclo[2,2,2]octane (DABCO) [2], and even a catalytic asymmetric version has been published [3]. During our own investigations of this simple and useful reaction [4], we found that in the reaction of aryl aldehydes with methyl vinyl ketone (MVK) catalyzed by DABCO, the reaction products are not as simple as those reported before. For  Molecules 2002, 7 722 example, using p-nitrobenzaldehyde (1.0 eq) and MVK (2.0 eq) as substrates