Palladium‐Catalysed Cross‐Coupling Reactions of Triorganoindium Reagents with Alkenyl Halides

Abstract

The regio-and stereoselectivity of the palladium-catalysed cross-coupling reactions of indium organometallics with stereodefined 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

Advances in Transition Metal (Pd,Ni,Fe)-Catalyzed Cross-Coupling Reactions Using Alkyl-organometallics as Reaction Partners

“…430 Triorganoindium reagents were stereospecifically coupled with stereodefined alkenyl iodides in good yields and short reaction times using Pd catalysts. Additionally, the Pd-catalyzed cross-coupling reaction of R 3 In (0.9 equiv) with 1,1-dibromo-1-alkenes gave coupling products in high yields (Figure 120).…”

Organoindium Reagents

“…Triorganoindium reagents (R 1 3 In; R 1 = alkyl, alkenyl, aryl and alkynyl) can be stereospecifically coupled with stereodefined alkenyl iodides in good yield and short reaction time under palladium catalysis. 11 (I) Lee and co-workers have developed an efficient method for the synthesis of various multialkynyl-substituted aromatic compounds using tetraalkynylindate organometallic species. 12 X In, LiCl …”

Bis(tri-tert-butylphosphine)palladium(0) [Pd(t-Bu3P)2]

“…Reductive elimination is also facilitated because of the bulky ligands. Thus 1 has been shown to be superior in transition-metalcatalyzed cross-coupling reactions compared to the classical [Pd(Ph 3 P) 4 ] catalyst. [Pd(t-Bu 3 P) 2 ] is not only efficient for typical cross-coupling reactions, such as Stille, Negishi, Suzuki, Heck, Sonogashira, or Buchwald-Hartwig aminations, with electrophiles R-X (X = Cl, Br, I, OTf, SO 2 Cl and others), but also for cross-coupling of organolithium reagents, 1 alkenylgermanes, 2 alkali-metal silanolates, 3 triorgano-indium reagents 4 and others.…”

“…Thus 1 has been shown to be superior in transition-metalcatalyzed cross-coupling reactions compared to the classical [Pd(Ph 3 P) 4 ] catalyst. [Pd(t-Bu 3 P) 2 ] is not only efficient for typical cross-coupling reactions, such as Stille, Negishi, Suzuki, Heck, Sonogashira, or Buchwald-Hartwig aminations, with electrophiles R-X (X = Cl, Br, I, OTf, SO 2 Cl and others), but also for cross-coupling of organolithium reagents, 1 alkenylgermanes, 2 alkali-metal silanolates, 3 triorgano-indium reagents 4 and others. Moreover, it has been used for arylations of hydro-siloxanes, 5 decarboxylative cross-coupling reactions, 6 carbonylations and amino-carbonylations, 7 carboiodinations, 8 C-H functionalizations, 9 cyanations, 10 methylenation of olefins 11 and annulation reactions.…”