Ene Reactions of Allylically Stannylated Cholestenes: Singlet Oxygenation of 7α-Triphenylstannylcholest-5-en-3β-ol, and of 7α-Triphenylstannyl- and 7α-Tributylstannyl-cholest-5-ene-3-one, and the Rearrangement of 5α-Tributylstannylperoxy-3β-benzyloxycholest-6-ene and of 7α-Trib...

DOI: 10.1039/P29920001095

Source and publish data:

Journal of the Chemical Society. Perkin transactions II p. 1095 - 1101 (1992)

Update date:2022-08-04

Topics:

Authors:

Dang, H.-S.

Davies, Alwyn G.

Read Full Text PDF DownLoad Join now for total 90,000,000 free articles

Article abstract of DOI:10.1039/P29920001095

The reaction of some allylically stannylated steroids with singlet oxygen has been investigated. 7α-Triphenylstannylcholest-4-ene-3β-ol reacts on the β-face with shift of the 4β-hydrogen to give 6β-hydroperoxy-7α-triphenylstannylcholest-4-ene-3β-ol, whereas cholest-5-ene-3β-ol itself reacts on the α-face to give 5α-hydroperoxycholest-6-ene-3β-ol. 7α-Triphenylstannyl- and 7α-tributylstannylcholest-5-ene-3-one give the corresponding 6β-hydroperoxy-7α-stannylcholest-4-ene-3-one (50-55percent), together with the 4,6-dien-3-one which is formed by elimination.In contrast, the parent cholest-5-en-3-one under the same conditions gives some of the 6β-hydroperoxy-4-ene-3-one, but the principal product is the hemiperketal from the 5α-hydroperoxycholest-6-ene-3-one.In neither system was there any evidence for a metalloene reaction, nor for cycloaddition accompanied by a nucleophilic 1,2-shift of the tin. 3β-Benzoyloxy-5α-tributylstannylperoxycholest-6-ene undergoes the Schenck and Smith types of rearrangement by a radical chain mechanism to give successively the corresponding 7α- and 7β-stannylperoxy-5-enes.

Full text of DOI:10.1039/P29920001095

View Article Online / Journal Homepage / Table of Contents for this issue

View Article Online

Products guided by the article

Product name:6β-hydroperoxy-3β-benzoyloxycholest-4-ene

Cas No:143657-36-7

R&D Labs maybe for 143657-36-7

Yingkou Sanzheng New Technology Chemical Industry Co., Ltd.

Contact:+86-417-2927806

Address:yingkou
ZCIC INTERNATIONAL LTD

Contact:+86-512-56795332

Address:No227 Shuanglong Rd, Fenghuang, Zhangjiagang
MedicalChem(Yancheng)Manuf.Co.,Ltd.

Contact:+86-515-84383366

Address:Touzeng BinHai, YanCheng City, JiangSu Province, China
suzhou chukai pharmateach co,.ltd

Contact:86-512-88812511

Address:Building 3, Wujiang Scientific Innovation Park, 2358 Changan Rd, Wujiang 215200, Jiangsu Province, P. R. China
Huaihua Baohua Biotechnology Co.,Ltd

website:http://www.baochengchem.com

Contact:86-519-82698291

Address:HouYang chemical development zone,Jintan,Jiangsu,China (213200)

Relevant to this article

Evidence on palladacycle-retaining pathway for Suzuki coupling. Inapplicability of Hg-drop test for palladacycle catalysed reactions

Doi:10.1016/j.jorganchem.2013.03.050
(2013)
Synthesis of pyrazolo[1,5-a]pyrimidine linked aminobenzothiazole conjugates as potential anticancer agents

Doi:10.1016/j.bmcl.2013.03.129
(2013)
Bodipy derivatives as organic triplet photosensitizers for aerobic photoorganocatalytic oxidative coupling of amines and photooxidation of dihydroxylnaphthalenes

Doi:10.1021/jo400769u
(2013)
Fabrication of deoxycholic acid tethered α-cyanostilbenes as smart low molecular weight gelators and AIEE probes for bio-imaging

Doi:10.1016/j.steroids.2020.108659
(2020)
Synthesis and platelet activating factor (PAF) receptor antagonist activity of 2,5-diarylcyclopentanol derivatives

Doi:10.1016/0223-5234(92)90156-U
(1992)
Synthesis of new heterotricyclic compounds containing the [1,8]naphthyridine group by thermal isomerization of 2-dialkylamino-3-vinylpyridines

Doi:10.1055/s-1992-26229
(1992)

Article Doi