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Synthesis 2011(9): 1321-1346  
DOI: 10.1055/s-0030-1258434
REVIEW
© Georg Thieme Verlag Stuttgart ˙ New York

Allylation of Imines and Their Derivatives with Organoboron Reagents: Stereocontrolled Synthesis of Homoallylic Amines

Timothy R. Ramadhar, Robert A. Batey*
Davenport Research Laboratories, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON, M5S 3H6, Canada
Fax: +1(416)9785059; e-Mail: rbatey@chem.utoronto.ca;
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Publication History

Received 9 November 2010
Publication Date:
11 February 2011 (online)

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Abstract

Homoallylic amines serve as important precursors for the synthesis of a variety of natural products and pharmaceutically relevant compounds. One widely used strategy for homoallylic amine synthesis is the addition of allylic metal or metalloid derivatives to imines or related functional groups. The use of allylic boron compounds for these reactions has emerged as an important synthe­tic approach, providing a robust and chemoselective method for efficient and stereocontrolled access to various homoallylic amines. In this review, a comprehensive and critical analysis of imine allyl­boration and crotylboration methods using organoborane, organoboronate and potassium organotrifluoroborate reagents is provided. These approaches include direct methods that accomplish diastereo- or enantiocontrolled addition of the organoboron species. Additionally, organoboron-based transition-metal-catalyzed allylation of imines and their respective surrogates using copper, indium, iridium, palladium or zinc catalysis is discussed. Finally, coverage on the use of allenyl- and propargylboron compounds and their application for the synthesis of homopropargylic and homoallenyl amines is provided.

1 Introduction

2 Organoborane Reagents

3 Organoboronic Acid and Ester Reagents

4 Potassium Organotrifluoroborate Reagents

5 Organoboron-Based Transition-Metal-Catalyzed Allylation

5.1 Copper Catalysis

5.2 Indium Catalysis

5.3 Iridium Catalysis

5.4 Palladium Catalysis

5.5 Zinc Catalysis

6 Allenylation and Propargylation Reactions

7 Concluding Remarks

Key words

allylation - amines - boron - imines - stereoselective synthesis

12

Boat-like transition state models 17 and 20 are shown in different conformations to the models shown in ref. 11 out of clarity. Enantiomeric transition states are not shown.