Highly Enantioselective Cross-Electrophile Aryl-Alkenylation of Unactivated Alkenes

Abstract

Enantioselective cross-electrophile reactions remain a challenging subject in metal catalysis, and with respect to data, studies have mainly focused on stereoconvergent reactions of racemic alkyl electrophiles. Here, we report an enantioselective cross-electrophile aryl-alkenylation reaction of unactivated alkenes. This method provides access to a number of biologically important chiral molecules such as dihydrobenzofurans, indolines, and indanes. The incorporated alkenyl group is suitable for further reactions that can lead to an increase in molecular diversity and complexity. The reaction proceeds under mild conditions at room temperature, and an easily accessible chiral pyrox ligand is used to afford products with high enantioselectivity. The synthetic utility of this method is demonstrated by enabling the modification of complex molecules such as peptides, indometacin, and steroids.

Nickel-Catalyzed Enantioselective Reductive Cross-Coupling Reactions

“…61 The reductive two-component couplings are thought to proceed via analogous mechanisms. 58,60 Oxidative addition of the aryl halide (42 or 45) followed by reduction is proposed to access a Ni(I)-aryl species. This intermediate can undergo migratory insertion of the pendant alkene, which may be the enantiodetermining step.…”

Ni-catalyzed cross-electrophile coupling between vinyl/aryl and alkyl sulfonates: synthesis of cycloalkenes and modification of peptides

“…While various cross-coupling methods have been developed for diversification of tyrosine in peptides,27 the introduction of an alkyl group via C–C bond formation remains largely unexplored. Moreover, unlike the conventional cross-coupling method that has been widely applied in this area,27,28 the potential of the cross-electrophile reaction for peptide modification is still waiting to be disclosed 29…”

Syntheses of 3,3-Disubstituted Dihydrobenzofurans, Indolines, Indolinones and Isochromanes by Palladium-Catalyzed Tandem Reaction Using Pd(PPh3)2Cl2/(±)-BINAP as a Catalytic System

“…The domino reactions of the synthesis of them were summarized mainly as follows: (i) the Pd or Ni-catalyzed cyclocarbopalladation/coupling fractions, in which the process was initiated by Heck cyclization of a starter (halide) and a relay (alkene), followed by intermolecular coupling reactions with a terminator (organometallic reagents, alkenes, alkynes, etc. ), including Suzuki, Stille, Heck, Sonogashira, C-H activation, carbonylation and amination and so forth [15][16][17]22,24,25,[29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44]; (ii) the C-H oxidative radical coupling reactions, in which these transformations were based on tandem radical addition/cyclization in the presence of oxidants with/without metal catalysts [18][19][20][21]23,26,[45][46][47][48][49][50][51][52][53][54][55]; and (iii) the other reactions [24,[56][57][58][5...…”