Organic Chemistry Portal

Abstracts

Search:

The Enantioselective Tsuji Allylation

Douglas C. Behenna and Brian M. Stoltz*

*Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, Email: stoltzcaltech.edu

D. C. Behenna, B. M. Stoltz, J. Am. Chem. Soc., 2004, 126, 15044-15045.

DOI: 10.1021/ja044812x


see article for more reactions

Abstract

Catalytic enantioselective examples of the Tsuji allylation using enol carbonates and enol silanes gave products possessing a quaternary stereogenic center, which are useful building blocks for synthetic chemistry.

see article for more examples



Details

The document discusses the development of the first catalytic enantioselective Tsuji allylations of simple alkanone derivatives by Douglas C. Behenna and Brian M. Stoltz at the California Institute of Technology. This method focuses on palladium-catalyzed enantioselective allylation, which is crucial for asymmetric catalysis. The researchers aimed to synthesize R-quaternary cycloalkanones, which are valuable chiral building blocks, using enol carbonates and silyl enol ethers. They found that mixed P/N-type ligands, particularly phosphino-oxazolines (PHOX), were effective in inducing high enantioselectivity and reactivity. The optimized conditions allowed for the allylation of various substituted cyclic ketones, producing chiral cycloalkanones with quaternary stereocenters in high enantiopurity and yield. The method was also applicable to seven- and eight-membered rings. The study demonstrated the versatility of these chiral building blocks through several synthetic transformations. The research was supported by various foundations and institutions, and the findings were published with detailed experimental procedures available online.


Deracemization of Quaternary Stereocenters by Pd-Catalyzed Enantioconvergent Decarboxylative Allylation of Racemic β-Ketoesters

J. T. Mohr, D. C. Behenna, A. M. Harned, B. M. Stoltz, Angew. Chem. Int. Ed., 2005, 44, 6924-6927.


Key Words

Tsuji-Trost Reaction, Ketones


ID: J48-Y2004-1830