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Synlett 2022; 33(15): 1556-1562
DOI: 10.1055/a-1855-3777
letter

Construction of Successive Stereogenic Centers of ent-Kauranoid through an Oxidative Dearomatization/1,2-Shift Cascade

Yuki Imamura
,
Hikaru Mizutani
,
Masahisa Nakada∗
This work was financially supported in part by JSPS KAKENHI Grants Numbers JP19H02725 and JP22H02087 and by a Waseda University Grant for Special Research Projects.
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Abstract

The construction of the successive stereogenic centers, including an all-carbon quaternary stereogenic center, of ent-kauranoid through an oxidative dearomatization/1,2-shift cascade is described. The developed cascade reaction of a substrate bearing a trans-2-(p-methoxyphenyl)vinyl group as the migrating group afforded the desired product in 83% yield. The 1,2-shift in the cascade is strongly affected by a stereoelectronic effect. The X-ray crystal structure of a compound bearing four successive stereogenic centers in the fused-ring moiety of ent-kauranoid diterpene, which was prepared by the oxidative dearomatization/1,2-shift cascade and subsequent stereoselective transformations, is also reported.

Key words

kauranoid - diterpenes - dearomatization - 1,2-shift reaction - quaternary carbon

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1855-3777.
  • Supporting Information


Publication History

Received: 23 April 2022

Accepted after revision: 18 May 2022

Accepted Manuscript online:
18 May 2022

Article published online:
15 June 2022

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