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Palladium‐Catalysed Cross‐Coupling Reactions of Triorganoindium Reagents with Alkenyl Halides
Author(s) -
Riveiros Ricardo,
Saya Lucía,
Pérez Sestelo José,
Sarandeses Luis A.
Publication year - 2008
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200701216
Subject(s) - chemistry , palladium , aryl , catalysis , reagent , coupling reaction , alkyl , medicinal chemistry , stereoselectivity , halide , alkyne , organic chemistry
The regio‐ and stereoselectivity of the palladium‐catalysed cross‐coupling reactions of indium organometallics withstereodefined 1‐haloalkenes and 1,1‐dihaloalkenes have been studied. Triorganoindium reagents (R 3 In; R = alkyl, alkenyl, aryl and alkynyl) can be stereospecifically coupled with stereodefined alkenyl iodides in good yields and short reaction times under palladium catalysis. Additionally, the palladium‐catalysed cross‐coupling reaction of R 3 In (90 mol‐%) with 1,1‐dibromo‐1‐alkenes gave dicoupling products in high yields. When the reaction was performed with 40 mol‐% of aryl‐, vinyl‐ and alkynylindium derivatives, trans ‐selective monosubstitution products were obtained in moderate to good yields. These selective couplings were performed with [Pd 2 dba 3 ]/P(2‐furyl) 3 (1:1, 2 mol‐%) at 0 °C or, for 1,1‐dibromo‐1‐alkenes with an aromatic group in the β‐position, [Pd(DPEPhos)Cl 2 ] (2 mol‐%) at room temperature as the catalytic system. The resulting ( Z )‐monobromoalkenes can be further functionalized by cross‐coupling reaction with various R 3 In (R = alkyl, aryl and alkynyl) in the presence of [Pd( t Bu 3 P) 2 ] as catalyst, at room temperature, to provide trisubstituted olefins in good yields.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)