Indole-3-methylamine (1) has been well demonstrated to be a very useful intermediate as a pharmaceutical building block and starting material for syntheses of phytoalexins.[1] The instability of indole-3-methylamine (...Indole-3-methylamine (1) has been well demonstrated to be a very useful intermediate as a pharmaceutical building block and starting material for syntheses of phytoalexins.[1] The instability of indole-3-methylamine (1) has undoubtedly restricted its application in synthetic chemistry. Hofmann rearrangement that directly converts carboxamides to alky carbamates in the presence of alcohol required unexceptionally a strong base,[2] which devaluated the possible usefulness of Hofmann rearrangement in preparation of base sensitive amines, especially for the preparation of unstable indole-3-methylamine (1). Herein we would like to report a convenient method for the preparation of alkyl carbamates of 1-protected indole-3-methylamines (4) via the diacetoxyiodobenzene (DIB) promoted Hofmann rearrangement under neutral condition.展开更多
As a versatile chiral ammonia equivalent, chiral tert-butylsulfinylamide (6) (TBSA) is a very useful auxiliary due to the characteristics of highly stereoselectivity in asymmetric induction and the sulfinyl group bein...As a versatile chiral ammonia equivalent, chiral tert-butylsulfinylamide (6) (TBSA) is a very useful auxiliary due to the characteristics of highly stereoselectivity in asymmetric induction and the sulfinyl group being easily removed compared with other amine auxiliaries since its introduction as a stable compound by Ellman in 1997.[1] Considering the importance of TBSA 6, search for efficient methods for the preparation of enantiopure TBSA (6) is the great interesting topic in synthetic chemistry. There were only three methods for the preparation of enantiopure TBSA (6) reported in the literature.[2] In this paper, we report an alternative three-step procedure to synthesize enantiopure TBSA (6) with a key step being the formation of tert-butylsulfinyloxazolidinone (4).……展开更多
基金Project supported by the National Natural Science Foundation of China (No. 20372048) and the Ministry of Education (EYTP).
文摘Indole-3-methylamine (1) has been well demonstrated to be a very useful intermediate as a pharmaceutical building block and starting material for syntheses of phytoalexins.[1] The instability of indole-3-methylamine (1) has undoubtedly restricted its application in synthetic chemistry. Hofmann rearrangement that directly converts carboxamides to alky carbamates in the presence of alcohol required unexceptionally a strong base,[2] which devaluated the possible usefulness of Hofmann rearrangement in preparation of base sensitive amines, especially for the preparation of unstable indole-3-methylamine (1). Herein we would like to report a convenient method for the preparation of alkyl carbamates of 1-protected indole-3-methylamines (4) via the diacetoxyiodobenzene (DIB) promoted Hofmann rearrangement under neutral condition.
基金Project supported by the National Natural Science Foundation of China (No. 20372048) and the Ministry of Education (EYTP).
文摘As a versatile chiral ammonia equivalent, chiral tert-butylsulfinylamide (6) (TBSA) is a very useful auxiliary due to the characteristics of highly stereoselectivity in asymmetric induction and the sulfinyl group being easily removed compared with other amine auxiliaries since its introduction as a stable compound by Ellman in 1997.[1] Considering the importance of TBSA 6, search for efficient methods for the preparation of enantiopure TBSA (6) is the great interesting topic in synthetic chemistry. There were only three methods for the preparation of enantiopure TBSA (6) reported in the literature.[2] In this paper, we report an alternative three-step procedure to synthesize enantiopure TBSA (6) with a key step being the formation of tert-butylsulfinyloxazolidinone (4).……
