39056-65-0Relevant academic research and scientific papers
One-step synthesis of 1-chloro-3-arylacetone derivatives from arylacetic acids
Zacuto, Michael J.,Dunn, Robert F.,Figus, Margaret
supporting information, p. 8917 - 8925 (2015/01/09)
A practical one-step method has been developed to prepare α-chloroketones from readily available, inexpensive phenylacetic acid derivatives. The method utilizes the unique reactivity of an intermediate Mg.enolate dianion, which displays selectivity for the carbonyl carbon of chloromethyl carbonyl electrophiles. Decarboxylation of the intermediate occurs spontaneously during the reaction quench. The utility of the reaction products has been demonstrated through the total synthesis of the natural product cimiracemate B.
Generation of 2-(Trimethylsiloxy)allyl Cations and Their Reactions with 1,3-Dienes. Change in Mechanism of 3 + 4 -> 7 Cycloaddition with Solvent
Shimizu, Nobujiro,Tanaka, Masayuki,Tsumo, Yuho
, p. 1330 - 1340 (2007/10/02)
A series of 12 different 2-(trimethylsiloxy)allyl cations 34a-l is generated from various 2-(trimethylsiloxy)allyl chlorides (3-5) with silver perchlorate.In nitromethane solution, all the cations smoothly react with furan and cyclopentadiene in a 3 + 4 -> 7 manner to give a comprehensive series of 8-oxabicyclooct-6-en-3-ones and bicyclooct-6-en-3-ones in good yields.The cycloaddition with furan proceeds in a stereospecific manner with the retention of allyl cation configurations, in accord with a concerted mechanism.The 3 + 4 -> 7 reactions in THF/ether contrast with those in nitromethane in the following ways. (1) The yield of the adducts strongly depends on the strusture of the allyl cations. (2) The reaction with furan is nonstereospecific. (3) An electrophilic substitution reaction strongly compets with the cycloaddition. (4) The cycloaddition between the cation 34a and 2-methylfuran is highly regioselective (11/12 = 19) as compared to that in nitromethane (the ratio being only 1.9).These findings in THF/ether are reasonably explained by a stepwise mechanism via an intermediate 40.Reactions with acyclic dienes (isoprene and 2,3-dimethylbutadiene), naphthalene, anisole, and methanol are also described.
