80423-30-9Relevant academic research and scientific papers
METHOD FOR PRODUCING SILYLENOL ETHERS
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Paragraph 0098; 0103, (2013/03/26)
The present invention provides a method for producing a silyl enol ether compound, which is convenient, has highly broad utility and places a low environmental load (less waste). The present invention relates to a method for producing silyl enol ether compound (3), including reacting ketone or aldehyde compound (1) with allylsilane compound (2) in the presence of a base and 0.00001 to 0.5 equivalents of an acid catalyst relative to ketone or aldehyde compound (1), wherein R1 is a hydrogen atom, an alkyl group, an aryl group or the like; R2 and R3 are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group or the like; R1 and R3, R1 and R2, or R2 and R3 optionally form a ring, together with the carbon atom(s) bonded thereto; R4 , R5 and R6 are each a hydrogen atom, an alkyl group or the like; two of R4, R5 and R6 optionally form a ring; R7, R8, R9, R10 and R11 are each a hydrogen atom, an alkyl group or the like; two of R7, R8, R9, R10 and R11 optionally form a ring.
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.
