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Synlett 2009(16): 2565-2582  
DOI: 10.1055/s-0029-1217747
ACCOUNT
© Georg Thieme Verlag Stuttgart ˙ New York

Catalytic Addition of Simple Alkenes to Carbonyl Compounds by Use of Group 10 Metals

Chun-Yu Ho*a, Kristin D. Schleicherb, Chun-Wa Chana, Timothy F. Jamison*b
a Center of Novel Functional Molecules, The Chinese University of Hong Kong, Shatin, NT, Hong Kong SAR, P. R. of China
Fax: +852 26035057; e-Mail: jasonhcy@cuhk.edu.hk;
b Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA
Fax: +1(617)3240253; e-Mail: tfj@mit.edu;
Further Information

Publication History

Received 25 March 2009
Publication Date:
04 September 2009 (online)

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Abstract

Recent advances using nickel complexes in the activation of unactivated monosubstituted olefins for catalytic intermolecular carbon-carbon bond-forming reactions with carbonyl compounds, such as simple aldehydes, isocyanates, and conjugated aldehydes and ketones, are discussed. In these reactions, the olefins function as vinyl- and allylmetal equivalents, providing a new strategy for organic synthesis. Current limitations and the outlook for this new strategy are also discussed.

1 Introduction

2 Carbonyl-Ene-Type Reactions

2.1 Reactions Catalyzed by Group 10 Cationic Complexes as Lewis Acids

2.2 Reactions Catalyzed by Low-Valent Nickel(0) Complexes

3 Unactivated Monosubstituted Alkenes as Vinylmetal Equivalents

3.1 Intramolecular Reactions with Aldehydes and Ketones

3.2 Intermolecular Reactions with Aldehydes

3.3 Synthesis of Acrylamides with Isocyanates

3.4 Conjugate Addition to α,β-Unsaturated Aldehydes and ­Ketones

4 Intramolecular Insertion of Alkenes into Cyclobutanones

5 Limitations and Outlook

Key words

alkenes - transition-metal catalysis - carbon-carbon bond formation - carbonyl-ene reactions - addition reactions

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12

For intramolecular examples of a carbonyl-ene reaction between monosubstituted alkenes and sterically demanding aldehydes, see refs. 10a and 10b.