Trimethylenemethane for Everyone: Convenient Preparation of the Nakamura-Yamago 1,3-Dipolar Reagent and an Effective Oxidative Transformation of Ketene Acetals
Delio Santalucia, Andrea Francesco Landucci, Nicolò Rossi, Alessandro Mandoli
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Abstract
A convenient route to the Nakamura-Yamago methylenecyclopropane (MCP) precursor 1 to oxygen-stabilized, singlet trimethylenemethane (TMM) is reported, which avoids the hurdles of the original preparation procedure. An effective oxidation protocol is also introduced for converting the sensitive ketene acetals (KAs) from 1,3-dipolar cycloaddition of 1 to electron-poor olefins, into the corresponding α-hydroxyesters. The method, based on the use of dimethyldioxirane (DMDO) in acetone, affords fair to good yields (23–81%) for a number of KAs endowed with ketone, ester, or imide functional groups, as well as additional C─C double bonds. The utility of the protocol is further exemplified by the diastereoselective preparation of the Rokach-Galano-Durand bicyclic lactone rac-18, one of the most versatile building-blocks for the synthesis of isoprostanoidic derivatives.
期刊介绍：
Organic chemistry is the fundamental science that stands at the heart of chemistry, biology, and materials science. Research in these areas is vigorous and truly international, with three major regions making almost equal contributions: America, Europe and Asia. Asia now has its own top international organic chemistry journal—the Asian Journal of Organic Chemistry (AsianJOC)
The AsianJOC is designed to be a top-ranked international research journal and publishes primary research as well as critical secondary information from authors across the world. The journal covers organic chemistry in its entirety. Authors and readers come from academia, the chemical industry, and government laboratories.
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