Tetrahedron p. 5685 - 5696 (1985)
Update date:2022-08-04
Topics:
Stuetz, Anton
Granitzer, Waltraud
Roth, Sabine
In exploring versatile synthetic routes to (E)-allylamine derivatives with antimycotic properties, a new method has been found in the trans-reduction of tertiary 2-alkinylanunes by diisobutylaluminum hydride (DIBAH). The stereoselectivity of this reaction, which is in contrast to the well-known cis-hydroalumination of disubstituted alkynes, and the regioselectivity have been studied in detail. Tertiary 2-alkinylamines 1 were generally reduced to (E)-2-alkenylamines 2 in toluene at 40°, and tertiary 2,4-alkadiynylamines 3 yielded a mixture of(E)-2-alken-4-ynylamines 4 and 2(E),4(Z)-alkadienylamines 5 in high stereochemical purity. This reduction was clearly different with respect to reactivity and selectivity in comparison with other reactions also proceeding via trans-hydroalumination, namely the lithium aluminum hydride reduction of α-hydroxyacetylenes and the reaction of alkynes with LiAlH(iso-Bu)2(n-Bu). Tertiary 6-hydroxy-2, 4-alkadiynylamines 10 were reduced to 6-hydroxy-2(E)-alken-4-ynylamines 11 with diisobutylaluminum hydride, whereas on treatment with lithium aluminum hydride 6-hydroxy-4(E)-alken-2-ynylamines 12 were obtained. LiAlH (iso-Bu)2(n-Bu) did not react with 2-alkinylamine 1a and the 2,4-alkadiynylamine 3a was only monohydroaluminated without discrimination of the two acetylene groups. A possible mechanism for the diisobutylaluminum hydride reduction of 2-alkinylamines is presented.
Guangzhou Chemical Reagent Factory
Contact:+86-20-8435 9820 or 8435 7345
Address:Southern Guangzhou, Guangdong, China
Zhejiang Quzhou Jiancheng Silicone Co., Ltd.(Shanghai Jiancheng Industial and Trade Co, Ltd)
Contact:18957018777 +86-570-3888777
Address:The company production base address： Quzhou City, Zhejiang Province high-tech industrial park Nianhua Road 37
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
Huangshan Violet Biological Technology Co., Ltd
Contact:+86-559-2335676
Address:16-201 JinShanYuan,JiangNan New City,TunXi District,HuangShan City,AnHui Province,China
Guangzhou Probig Fine Chemical Co., Ltd.
Contact:020-86297874
Address:No.2, 1/F, No.20, Hetai Road,Hebian Village, Baiyun District,Guangzhou,China
Doi:10.1021/ja01503a052
(1960)Doi:10.1002/ardp.19552880710
(1955)Doi:10.1017/S0317167100002274
(1951)Doi:10.1007/BF00911439
()Doi:10.1021/ja00272a027
(1986)Doi:10.1002/jhet.5570330325
(1996)
