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Pure Appl. Chem., 2006, Vol. 78, No. 7, pp. 1397-1406

Recent developments in the chiral synthesis of homoallylic amines via organoboranes

P. Veeraraghavan Ramachandran and Thomas E. Burghardt

Herbert C. Brown Center for Borane Research, Department of Chemistry,Purdue University, 560 Oval Dr., West Lafayette, IN 47907-2084, USA

Abstract: Among the plethora of protocols for the preparation of chiral homoallylic amines, the use of boron-based reagents remains relatively undeveloped. However, the recent advances in the use of α-pinene-based versatile reagents for the synthesis of such amines confirmed that very high enantioselectivity and outstanding diastereoselectivity can be readily achieved. Addition of the "allyl"boron reagents to various N-substituted imines provided the desired amine products in high yields and high to very high ee. The discovery that an addition of 1.0 equiv of methanol or water to the "allyl"boration reaction with N-masked imines is critical allowed for higher yields and noticeably improved ee. The use of N-aluminoimines, which are not only easy to prepare by a partial reduction of nitriles, but are also relatively stable for both enolizable and non-enolizable substrates, considerably expanded the scope of the reactions. In this review, the developments in the syntheses of chiral homoallylic amines using organoboranes, with the particular accent on the reagent-controlled reactions, are summarized. Additionally, the novel methodology for the crotyl- and alkoxyallylboration of imines using trialkylboron "ate" complexes is described.