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 MoreXi'an North Information Industry Co., Ltd. Weilv Chemical Department
Contact:+86-29-88156413
Address:Jixiang Road 99 Xi'an Shaanxi Province
Nanjing distinctions Medical Technology Co., Ltd.(expird)
Contact:+86-15996203785 13914714059
Address:nanjing,jiangsu , China
Chongqing maohuan Chemicals Co., Ltd
website:http://www.bschem.com
Contact:+86 13996103726
Address:Chongqing Nan'an District Tu Town
Shanghai AoBo Bio-Pharmaceutical Technology Co., Ltd.
Contact:+86-21-51320130-801, 816
Address:Room 601, No. 1011, Halei Road, Zhangjiang High-Tech Park, Pudong, Shanghai
Shenzhen Hongyuan Import & Export Co., Ltd.
Contact:0755-26407171
Address:Shenzhen Hongyuan Chemical New Materials Technology Co., Ltd.
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)
