Journal of the Chemical Society. Perkin transactions I p. 1549 - 1556 (1981)
Update date:2022-07-30
Topics:
Fleming, Ian
Michael, Joseph P.
As part of a projected synthesis of gelsemine (1), the synthesis of dimethyl 7-oxobicyclo<2.2.1>hept-5-ene-2-endo,3-exo-dicarboxylate (5) is described.The route involves the silicon-controlled rearrangement of 5-exo-bromo-3-exo-methoxycarbonyl-7-anti-trimethylsilylbicyclo<2.2.1>heptane-2,6-carbolactone (9), catalysed by silver ions in methanol, to give dimethyl 7-syn-hydroxybicyclo<2.2.1>hept-5-ene-2-endo,3-exo-dicarboxylate (11).Some related reactions show that a 7-trimethylsilyl group in a norbornene can be used to synthesise other 7-functionalised norbornenes.Thus the epoxide (13) of methyl 7-anty-trimethylsilylbicyclo<2.2.1>hept-5-ene-2-endo-carboxylate (12) rearranges on treatment with boron trifluoride-ether to give methyl 7-anti-hydroxybicyclo<2.2.1>hept-5-ene-2-exo-carboxylate (14), and treatment of (12) with bromine gives mainly the rearranged bromide, methyl 7-anti-bromobicyclo<2.2.1>hept-5-ene-2-exo-carboxylate (16).Some limitations in this approach to 7-functionalised norbornenes are also described.
View Morewebsite:http://www.shtopchem.com/
Contact:0086-0576-87776998
Address:room no 1608,xuhui business building yude road,xujiahui street, xuhui district
Taimai Sanluck Pharmaceutical Co.,Ltd
Contact:86-592-7662921
Address:8D,No.186,Huarong Road,Huli,Xiamen,China
VanderArk International Limited
Contact:86-10-82437576
Address:Qing He
Contact:+86-571-86025531 / 86024803
Address:1218-24 Guangyin Mansion,42 Fengqi East Road
Wuhan Chemwish Technology Co., Ltd
website:http://www.chemwish.com/
Contact:+86-27-67849912
Address:Room 1311, Unit 2, Block1, Innovation Road East Lake High-tech Development Zone Wuhan, Hubei，P.R. China
Doi:10.1055/s-2000-8235
(2000)Doi:10.1055/s-1981-29487
(1981)Doi:10.1055/s-2002-20962
(2002)Doi:10.1016/S0040-4039(01)90476-9
(1981)Doi:10.1021/ja00430a027
(1976)Doi:10.1007/BF00741734
(1967)
