☆ 4.8 Article

Enantioselective Synthesis of Isocarbostyril Alkaloids and Analogs Using Catalytic Dearomative Functionalization of Benzene

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2019)

期刊

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

卷 141, 期 1, 页码 657-670

出版社

AMER CHEMICAL SOC

DOI: 10.1021/jacs.8b12123

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Chemistry, Multidisciplinary

资金

University of Illinois
NIH/National Institute of General Medical Sciences [GM122891]
ACS Petroleum Research Fund [57175-DNI1]
NIH-NIGMS CBI Training Grant [T32-GM070421]
NSF

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Enantioselective total syntheses of the anticancer isocarbostyril alkaloids (+)-7-deoxypancratistatin, (+)-pancratistatin, (+)-lycoricidine, and (+)-narciclasine are described. Our strategy for accessing this unique class of natural products is based on the development of a Nicatalyzed dearomative trans-1,2-carboamination of benzene. The effectiveness of this dearomatization approach is notable, as only two additional olefin functionalizations are needed to construct the fully decorated aminocyclitol cores of these alkaloids. Installation of the lactam ring has been achieved through several pathways and a direct interconversion between natural products was established via a late-stage C-7 cupration. Using this synthetic blueprint, we were able to produce natural products on a gram scale and provide tailored analogs with improved activity, solubility, and metabolic stability.

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