The stereospecific cross-coupling of enantioenriched non-benzylic secondary alkyl boron compounds has been achieved. The high selectivity toward product formation over an undesired β-H elimination pathway is achieved via an intramolecular coordination of an ancillary carbonyl to the metal center in the diorganopalladium intermediate.

[reaction: see text] A Pd-catalyzed coupling of enol tosylates and amides has been developed. Ligand screening revealed dipf as the most general ligand for this transformation. A variety of enol tosylates were coupled to an array of enamides in 58-97% yield.

The indole nucleus is a common and important feature of a variety of natural products and medicinal agents. 1 The traditional approach for preparing the indole nucleus is the Fischer indole reaction. 2 As this reaction has shortcomings, the palladium-catalyzed coupling of ohaloanilines is becoming an excellent alternative. 3 A combination of such a palladium-catalyzed reaction with ketones and aldehydes would be a tremendously straightforward approach 4 (Scheme 1). Herein, we wish to disclose a new and efficient method for indole synthesis using a palladium-catalyzed annulation between o-iodoanilines and ketones.The reaction would necessarily proceed by enamine formation 4 followed by an intramolecular Heck reaction 5 (Scheme 1). In our search for the appropriate reaction conditions, we found that an amine base was critical to the successful coupling. However, in the palladiumcatalyzed coupling of the iodoaniline 1c (R 1 ) 1-(1,2,4triazolyl)methyl) 6 and cyclohexanone with diisopropylamine as base the byproduct 2-methylindole 2 (∼9%) was generated. The formation of the byproduct is a result of the ability of palladium to oxidize the amine, 7 generating Pd(0) and the imine/enamine of isopropylamine and acetone. Transamination with 1c and Heck coupling provided 2

N-H ketoimines 3a-3v are readily prepared in high yield via organometallic addition to nitriles and isolated as corresponding bench-stable hydrochloride salts. Homogeneous asymmetric hydrogenation of unprotected N-H ketoimines 3a-3v using Ir-(S,S)-f-binaphane as catalyst provides chiral amines 4a-4v in 90-95% yield with enantioselectivities up to 95% ee.