Journal of the Chemical Society. Perkin transactions I p. 3272 - 3278 (1981)
Update date:2022-08-04
Topics:
Bloodworth, A. J.
Eggelte Henny J.
Cyclopent-3-enyl hydroperoxide (9) has been prepared from cyclopentadiene via hydroboration and autoxidation, and converted by bromination into trans-3,cis-4-dibromocyclopentyl hydroperoxide (10).Reaction of compound (10) with silver oxide has afforded endo-5-bromo-2,3-dioxabicyclo<2.2.1>heptane (11) (42percent), whereas treatment of compound (10) with silver trifluoroacetate has provided exo-5-bromo-2,3-dioxabicyclo<2.2.1>heptane (15) (6percent) and exo-5-trifluoroacetoxy-2,3-dioxabicyclo<2.2.1>heptane (16) (14percent).The exo-bromide (15) (11percent) has also been prepared from cyclopent-3-enyl bromide by trans-hydroperoxybromination and ring closure with silver oxide.The configurations of the <2.2.1>peroxides have been confirmed by catalytic hydrogenation.Cyclohex-3-enyl hydroperoxide (26) has been prepared from anisole by a 5-step procedure ending with oxidation of N-cyclohex-3-enyl-N'-tosylhydrzide, and converted by bromination into a mixture of two diastereoisomeric 3,4-dibromocyclohexyl hydroperoxides.Treatment of the trans-3,cis-4-dibromide (27) with silver oxide has afforded endo-2-bromo-6,7-dioxabicyclo<3.2.1>octane (29) (40percent), whereas reaction of the cis-3,trans-4-dibromide (28) with silver trifluoroacetate has provided exo-2-bromo-6,7-dioxabicyclo<3.2.1>octane (30) (18percent).Treatment of compound (27) with silver trifluoroacetate yielded a 9:1 mixture of peroxides (30) and (29) (19percent), but compound (28) did not react with silver oxide.It is suggested that the silver oxide-induced dioxabicyclizations proceed by an SN2 mechanism whereas the silver trifluoroacetate reactions involve a bromonium ion intermediate.
View MoreChengdu NoVi Biotechnology Co., Ltd.(expird)
Contact:13551243286/028-81458053
Address:NO.168-1-224 JULONG ROAD WUHOU DISTRICT, CHENGDU CITY,SICHUAN PROVINCE
Xi'an Unique Electronic and Chemical Co., Ltd.
Contact:+86-029-88238008
Address:1703# B BUILDING WEST ELECTRONIC ZONE, XI'AN, CHINA
Wuxi Pharma-Trading Import & Export Co.,Ltd.
Contact:+86-510-82304590 82716390
Address:Room 523,Youzu Alliance Building,No.88 Renmin Zhonglu,Wuxi,Jiangsu,China
Contact:+86-10-83993285
Address:Rm.1708, Haobai Tower, Building 6, No.50, North Road, West Third Ring, Haidian District, Beijing, China
Jinan Kaypharm Chemical Co.,Ltd
Contact:86-0531-86986780
Address:Room101,No189-2,Huayuan Road,Jinan City,Shandong Province
Doi:10.1080/00397919308018594
(1993)Doi:10.1039/b001119n
(2000)Doi:10.1248/yakushi1947.90.5_629
(1970)Doi:10.1016/S0022-328X(98)01137-1
(1999)Doi:10.1039/a707857i
(1998)Doi:10.1016/j.bmc.2004.01.039
(2004)
