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Synthesis 2022; 54(21): 4691-4702
DOI: 10.1055/a-1799-0459
DOI: 10.1055/a-1799-0459
special topic
Asymmetric C–H Functionalization
Eight-Step Asymmetric Synthesis of (–)-Berkelic Acid
Authors
This work is supported by the Fundamental Research Funds for the Central Universities (2042020kf0039 and 2042021kf0214), the National Natural Science Foundation of China (Grants 21801193, 21871213, and 22071189) and the startup funding from Wuhan University.
Abstract
We herein report an eight-step asymmetric synthesis of (–)-berkelic acid. This work features a sequential Catellani-type reaction/oxa-Michael addition with epoxides as dual-functionalized alkylating reagents for synthesizing the isochroman framework, a one-pot, acid-catalyzed deprotection/spiroacetalization process for the construction of a tetracyclic core intermediate, and a late-stage Ni-catalyzed reductive coupling reaction for the installation of the side chain. Remarkably, during the deprotection/spiroacetalization process, four new stereocenters are created with high stereocontrol from a single existing chiral center.
Key words
(–)-berkelic acid - total synthesis - Catellani reaction - C–H activation - spiroacetalization - reductive couplingSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1799-0459.
- Supporting Information (PDF) (opens in new window)
Publication History
Received: 25 February 2022
Accepted after revision: 15 March 2022
Accepted Manuscript online:
15 March 2022
Article published online:
19 May 2022
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For selected total synthesis examples applying the Catellani-type reaction as the key step, see:
For selected reviews, see:
For selected recent examples, see: