Journal of the Chemical Society. Perkin transactions I p. 236 - 250 (1981)
Update date:2022-08-05
Topics:
Suginome, Hiroshi
Furusaki, Akio
Kato, Kimitoshi
Maeda, Norio
Yonebayashi, Fumihiko
Hypoiodites of cholesterol and epicholesterol in benzene containing mercury (II) oxide and iodine underwent photo-induced rearrangement to give 3α,5-epoxy-6β- and -6α-iodo-A-homo-4-oxa-5α-cholestanes (3) and (4), together with 3-formyloxy-2-iodo-A-nor-2,3-secocholest-5-ene (2).Stereochemistry of the epoxide (3) was established by an X-ray crystallographic analysis.When the reaction of cholesterol hypoiodite was induced thermally at 55-60 deg C, only the 6β-isomer, accompanied by cholest-5-en-3α-yl A-homo-4-oxacholest-5-en-3α-yl ether (20) and A-homo-4-oxacholest-5-en-3α-ol (21), is formed.Catalytic hydrogenolysis of iodo-epoxide (3) or (4) gave 3α,5-epoxy-A-homo-4-oxa-5β-cholestane (16) which was transformed into 2-acetyl-5-acetoxymethyl-4-oxa-5β-cholest-2-ene (29) upon treatment with boron trifluoride-ether-acetic anhydride in benzene.In contrast, the newly synthesized hypoiodite of 3α,4,4-trimethylcholest-5-en-3β-ol, in benzene containing mercury (II) oxide and iodine, gave 2-acetyl-3-oxacholest-5-enes (26) and (27) together with 3α,5α-epoxy-A-homo-4-oxasteroids (24) and (25) on irradiation or thermolysis.The formation of the products (26) and (27) indicates the intervention of a common oxyl radical (E) in the rearrangements of 3-hydroxy-Δ5-steroid hypoiodites to products (3), (4), (24), (25), (26), and (27).The pathways of the rearrangements and the stereoselectivity of the reactions are discussed.
View MoreXi'an Galaxy Chemicals CO., Ltd
Contact:86-29-89380370
Address:No.8, Gaoxin three road, Xi'an city.
SICHUAN TONGSHENG AMINOACID CO.LTD
website:http://www.aminoacid.cc
Contact:86-838-2274206/2850606
Address:Room 1-11-1,No.19 of North TianShan Road,Deyang,Sichuan China
XI'AN CHUKANG BIOTECHNOLOGY CO.,LTD
Contact:29-63685658 63685359
Address:Room 3-1202,Building 1,Oriental oasis,East of Xianning Road,Xi'an,Shaanxi 710043 P.R.China
Winchem Industrial Co. Ltd.(expird)
Contact:86-574-83851061 86-574-87083208
Address:Room 905, No.3 Building,East Business Center, 456 Xingning Road, Ningbo City,China
Chengdu Green Young Biopharmaceutical INC
Contact:+86-28-85337952
Address:1-B-26,Tianhe Industry Park, No.1480 of Tianfu Road,Chengdu,P.R.China,610000
Doi:10.1016/j.molstruc.2011.09.024
(2011)Doi:10.1002/ardp.19753081103
(1975)Doi:10.1016/j.molstruc.2020.129430
(2021)Doi:10.1002/ejoc.201800554
(2018)Doi:10.1021/jo00872a018
(1976)Doi:10.1016/j.tetlet.2007.02.024
(2007)
