Asymmetric Heck reaction

作者：Shibasaki M^*; Vogl EM; Ohshima T

来源：Advanced Synthesis & Catalysis, 2004, 346(13-15): 1533-1552.

DOI：10.1002/adsc.200404203

• asymmetric catalysis
• carbon-carbon bond-forming reaction
• chiral ligand
• Heck reaction
• homogeneous catalysis
• natural product synthesis

The asymmetric Heck reaction is a powerful method for the synthesis of both tertiary and quaternary chiral carbon centers, with an enantiomeric excess often greater than 80%, and in some cases much higher (up to 99% ee). A variety of carbocyclic and heterocyclic systems can be constructed, including spirocyclic systems. The scope of the reaction with respect to the product alkene isomerization is somewhat limited by problems of regioselectivity, however, these problems are surmountable, and a new generation of ligands that dissociate more rapidly from the products, might improve both enantio- and regiocontrol. A variety of chiral compounds prepared by the asymmetric Heck reaction were successfully utilized in the enantioselective syntheses of complex natural products.
1 Introduction
2 Mechanism
2.1 Regioselectivity
2.2 Enantioselectivity
3 Intramolecular Reaction
3.1 Formation of Tertiary Carbon Centers
3.2 Formation of Quaternary Carbon Centers
4 Intermolecular Reaction
4.1 Dihydrofurans and Cyclic Enol Ethers
4.2 Dihydropyrroles
4.3 Dihydrodioxepins
4.4 Hydroarylations of [2.2.1] Bicyclics
5 New Chiral Ligands
5.1, P,N Ligands
5.2 N,N Ligands
5.3 PP Ligands and Derivatives
5.4 Other Types of Ligands and Diastereoselective Reactions
6 Methodological Developments
7 Summary and Conclusions.

• 出版日期2004-12