Total synthesis of myriocin and mycestericin D employing Rh(II)-catalyzed CH amination followed by stereoselective alkylation

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• 作者：Narumi Noda^a ; Hisanori Nambu^a ; Kana Ubukata^a ; Tomoya Fujiwara^a ; Kiyoshi Tsuge^b ; Takayuki Yakura^a ; ^{yakura@pha.u-toyama.ac.jp}
• 关键词：Total synthesis ; CH amination ; Alkylation ; Cross metathesis ; Rhodium
• 刊名：Tetrahedron
• 出版年：2017
• 出版时间：16 February 2017
• 年：2017
• 卷：73
• 期：7
• 页码：868-878
• 全文大小：1058 K
• 卷排序：73

文摘

Total synthesis of myriocin and mycestericin D was achieved using the Du Bois Rh(II)-catalyzed CH amination of a sulfamate and subsequent alkylation as a key step. The reaction of a sulfamate with PhI(OAc)2 and MgO in the presence of Rh2(OAc)4 gave oxathiazinane N,O-acetal as the sole product in high yield. Alkylation of N,O-acetal using vinylmagnesium bromide in the presence of ZnCl2 proceeded stereoselectively to provide an oxathiazinane bearing a quaternary chiral center in high yield. Myriocin and mycestericin D were synthesized from a common synthetic intermediate. This route includes the first application of the Du Bois procedure for constructing a quaternary chiral center.