This article demonstrates a catalytic method for C(aryl)-C(alkyl) bond functionalization of N-sulfonyl amines. A cobalt(III)catalyst was used to cleave the C-C bond via β-carbon elimination, providing a metallacycle ...This article demonstrates a catalytic method for C(aryl)-C(alkyl) bond functionalization of N-sulfonyl amines. A cobalt(III)catalyst was used to cleave the C-C bond via β-carbon elimination, providing a metallacycle intermediate. Subsequent allylation,amidation, or alkenylation of the intermediate led to divergent conversions in the presence of diverse coupling partners. when the coupling partner was a diene, an insertion-type functionalization was realized with an exclusive 1,3-regioselectivity, in which both of the fragments derived from N-sulfonyl amines were utilized.展开更多
杨梅素是一种主要用于抗炎的多酚类黄酮化合物,为改善其水溶性和稳定性,合成了杨梅素-3-O-β-D-乳糖,并开发了一条高效的合成路线。首先以杨梅苷为起始原料,对杨梅苷的5位、7位、3′位、4′位和5′位酚羟基进行保护,形成五苄基保护的杨...杨梅素是一种主要用于抗炎的多酚类黄酮化合物,为改善其水溶性和稳定性,合成了杨梅素-3-O-β-D-乳糖,并开发了一条高效的合成路线。首先以杨梅苷为起始原料,对杨梅苷的5位、7位、3′位、4′位和5′位酚羟基进行保护,形成五苄基保护的杨梅苷。然后脱除3位鼠李糖,再与乙酰基保护的乳糖溴苷反应,最后通过依次脱去乙酰基和苄基得到目标化合物。经过路径优化,最终以更高效的方法合成了杨梅素-3-O-β-D-乳糖,减少了副产物的生成,提高了原合成路线总收率,此方法的总产率为44.5%。该路径得到了2个新型的杨梅素衍生物中间体。目标化合物的结构均经过1 H NMR,13 C NMR和HR-MS(ESI)确证。展开更多
基金supported by the“Pioneer”and“Leading Goose”R&D Program of Zhejiang(2022SDXHDX0006)the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(2020R01004)。
文摘This article demonstrates a catalytic method for C(aryl)-C(alkyl) bond functionalization of N-sulfonyl amines. A cobalt(III)catalyst was used to cleave the C-C bond via β-carbon elimination, providing a metallacycle intermediate. Subsequent allylation,amidation, or alkenylation of the intermediate led to divergent conversions in the presence of diverse coupling partners. when the coupling partner was a diene, an insertion-type functionalization was realized with an exclusive 1,3-regioselectivity, in which both of the fragments derived from N-sulfonyl amines were utilized.
文摘杨梅素是一种主要用于抗炎的多酚类黄酮化合物,为改善其水溶性和稳定性,合成了杨梅素-3-O-β-D-乳糖,并开发了一条高效的合成路线。首先以杨梅苷为起始原料,对杨梅苷的5位、7位、3′位、4′位和5′位酚羟基进行保护,形成五苄基保护的杨梅苷。然后脱除3位鼠李糖,再与乙酰基保护的乳糖溴苷反应,最后通过依次脱去乙酰基和苄基得到目标化合物。经过路径优化,最终以更高效的方法合成了杨梅素-3-O-β-D-乳糖,减少了副产物的生成,提高了原合成路线总收率,此方法的总产率为44.5%。该路径得到了2个新型的杨梅素衍生物中间体。目标化合物的结构均经过1 H NMR,13 C NMR和HR-MS(ESI)确证。
