Journal of the Chemical Society. Perkin transactions I p. 2415 - 2434 (1981)
Update date:2022-08-05
Topics:
Carter, Martin J.
Fleming, Ian
Percival, Alan
The synthesis and Diels-Alder reactions of 1-trimethylsilylbutadiene (3) and its 3-methyl (17), 3-trimethylsilyloxy (20), 4-methyl (4), and 4-trimethylsilyl (6) derivatives are reported.The silyl group reduces somewhat the rate of the Diels-Alder reactions, and has, if anything, a small 'ortho'-directing effect on the regioselectivity in the reactions of (3) with methyl acylate, methyl propiolate, citraconic anhydride, and 2,6-dimethylbenzoquinone.The other substituent in the dienes (17), (20), and (4) is therefore the major influence on the regioselectivity in the reactions of these dienes with methyl acrylate and methyl propiolate.The products of the Diels-Alder reactions of (3), (17), and (4) are allylsilanes, which undergo clean protodesilylation with acid, and, with the acid and ester derived from the maleic anhydride adduct of (3), undergo epoxidation and sulphenylation reactions giving an allyl alcohol (33) and an allyl sulphide (37), respectively.The adducts from (20) can be hydrolysed to β-silylketones, which can be converted into enones by bromination. 1-Pentamethyldisilylbutadiene (15) is no more reactive and no more regioselective than (3).The 'ortho'-adduct (42) from the reaction of (3) and methyl propiolate aromatises with DDQ to give methyl m-trimethylsilylbenzoate (53) in high yield, in a reaction involving rearrangement of the silyl group, even though a direct dehydrogenation is an available pathway.
View MoreSHANGHAI SYSTEAM BIOCHEM CO., LTD
website:http://www.systeambc.com
Contact:86-021-58380978
Address:Building 87,Lane 669, Dong Jing Road Shanghai,P.R.China
website:http://www.lonwinchem.com
Contact:Tel: 86-21-59858395
Address:No#966,Huaxu Road,Shanghai 201702,P.R.China
Xiamen Goodhealth Pharmchem Co., Ltd.
Contact:0086-592-2097683
Address:404R No.2 54# Minzu Rd., Xiamen, China
Contact:+86 021-51698675
Address:1701, Jielong Plaza, No.618 Pingliang Rd, ShangHai,China
Contact:086-027-83820093
Address:16#luojiashan, wuchang district
Doi:10.1021/ja00369a021
(1982)Doi:10.1039/c39810001030
(1981)Doi:10.1016/S0040-4039(01)81993-6
(1981)Doi:10.1002/jlac.198119811211
(1981)Doi:10.1039/c8ra00564h
(2018)Doi:10.1016/j.bmcl.2004.09.002
(2004)