Abstract
The purpose of this review is to update (publications from 1981 to mid 2006) the synthetic applications of dealkoxycarbonylations of malonate esters, β-keto esters (and related esters with α-substituted electron-withdrawing functionalities) induced by heating with water or with water in the presence of salts (such as NaCN, NaCl or LiCl) in dipolar aprotic solvents. The presentation will be divided in two parts. In Part 1, discussion will focus on the dealkoxycarbonylations of malonate esters. Part 2 (to follow as a separate paper) will deal with the dealkoxycarbonylations of β-keto esters and α-cyano esters (and related analogues).
Highlights
Activated esters, which include such substrates as malonates, β-ketoesters and α-cyanoesters, are of considerable importance in organic synthesis
We have reported in a number a publications that these substrates undergo dealkoxycarbonylations on being heated in dipolar aprotic solvents in the presence of water, or in some substrates with water in the presence of added salts to yield the corresponding esters, ketones and nitriles
This overall process is a formal loss of CO2R and protonation of the intermediate carbanion
Summary
Activated esters, which include such substrates as malonates, β-ketoesters and α-cyanoesters, are of considerable importance in organic synthesis. We have reported in a number a publications that these substrates (and other activated analogues) undergo dealkoxycarbonylations on being heated in dipolar aprotic solvents (such as DMSO or DMF) in the presence of water, or in some substrates with water in the presence of added salts (such as NaCN, NaCl or LiCl) to yield the corresponding esters, ketones and nitriles. This procedure is facile, avoids harsh acidic and ISSN 1424-6376. Alkaline conditions and tolerates many protecting groups This methodology is much more convenient than the classical procedures for accomplishing these transformations. Because of the large numbers of published papers, the author is going to be somewhat selective in the illustrative synthetic examples chosen from the literature
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
