Journal of Organic Chemistry p. 2781 - 2787 (1991)
Update date:2022-07-29
Topics:
Back, Thomas G.
Muralidharan, K. Raman
Benzeneselenenyl p-toluenesulfonate (1) was generated in situ by the reaction of silver p-toluenesulfonate with benzeneselenenyl chloride in acetonitrile.The reagent reacted with acetylenes by electrophilic 1,2-addition to afford the β-(phenylseleno)vinyl p-toluenesulfonates 2-12, generally in high yield.The latter were formed preferentially by anti addition, but with poor regioselectivity, unless a strongly orienting group (e.g., phenyl) was present.Selenenyl sulfonate 1 was also unexpectedly produced via radical pathways by heating p-toluenesulfonic acid with AIBN in the presence of diphenyl diselenide, or from the pyrolysis of sulfinyl sulfone 15 with the diselenide.The regioisomeric adducts 3 and 4 were prepared from 1 and 1-decyne, and both underwent elimination with potassium tert-butoxide to afford the acetylenic selenide 19 initially, which isomerized to a 6:1 mixture of the propargylic and allenic selenides 20 and 21 upon further equilibration.A Fritsch-Buttenberg-Wiechell rearrangement is proposed for the elimination of 4.The syn elimination of the selenoxide of 4 required forcing conditions and afforded only ca. 20percent of the corresponding allenic sulfonate 22.The electrophile 1 induced the efficient cyclization of 5-hexen-1-ol and 4-pentenoic acid to the corresponding pyran 24 and lactone 25, respectively.It failed to cyclize alkynols, but afforded the lactones 28 and 29 from 4-pentynoic acid in low yield.
View MoreShenyang Mole pharmaceutical Technology Development Co.,Ltd
Contact:+86-24-31204918/13889278616
Address:No.44, wanliutang road, shenhe District of Shenyang
Taizhou Sunny Chemical Co.,Ltd
Contact:+86-523-86920899 +86-13951172783
Address:No.11 Xingyuang road, Gaoyong Chemical Industry Park, Gaogang Jiangsu China
Wudi Reaction Pharma&Chemical Co.,Ltd.
website:http://www.ruixinchem.com/
Contact:86-543-2257986
Address:Xinhai Industrial Zone, Wudi County,Shandong Province,China.
website:http://www.uvchemkleys.com
Contact:+86 21 3868 0172
Address:RM-1203, Ziguang Building, #341 Shangcheng Road, Pudong Dist, Shanghai
Contact:+36(21)2523420
Address:Head office: 1102 Budapest, SZENT LASZLO TER 24/B. 1/1., HUNGARY / CHINA
Doi:10.1021/ol901302d
(2009)Doi:10.1002/ejoc.201100654
(2011)Doi:10.1002/ejic.201100341
(2011)Doi:10.3762/bjoc.7.140
(2011)Doi:10.1039/c1cc13684d
(2011)Doi:10.1016/j.ejmech.2011.06.005
(2011)