Mechanism of NHC-Catalyzed Conjugate Additions of Diboron and Borosilane Reagents to α,β-Unsaturated Carbonyl Compounds.
Broadly applicable enantioselective C-B and C-Si bond-forming processes catalyzed by an N-heterocyclic carbene (NHC) were recently introduced; these boryl and silyl conjugate addition reactions (BCA and SCA, respectively), which proceed without the need for a transition-metal complex, represent reaction pathways that are distinct from those facilitated by transition-metal-containing species (e.g., Cu, Ni, Pt, Pd, or Rh based). The Lewis-base-catalyzed (NHC) transformations are valuable to chemical synthesis, as they can generate high enantioselectivities and possess unique chemoselectivity profiles. Here, the results of investigations that elucidate the principal features of the NHC-catalyzed BCA and SCA processes are detailed. Spectroscopic evidence is provided illustrating why the presence of excess base and MeOH or H2O is required for efficient and enantioselective boryl and silyl addition reactions. It is demonstrated that the proton sources influence the efficiency and/or enantioselectivity of NHC-catalyzed enantioselective transformations in several ways. The positive, and at times adverse, impact of water (biphasic conditions) on catalytic enantioselective silyl addition reactions is analyzed. It is shown that a proton source can facilitate nonenantioselective background reactions and NHC decomposition, requiring the catalyst to surpass such complications. Stereochemical models are presented that account for the identity of the observed major enantiomers, providing a rationale for the differences in selectivity profiles of BCA and SCA processes.
Department of Chemistry, Merkert Chemistry Center, Boston College , Chestnut Hill, Massachusetts 02467, United States.
Hao
H
Wu
Department of Chemistry, Merkert Chemistry Center, Boston College , Chestnut Hill, Massachusetts 02467, United States.
Jeannette M
JM
Garcia
Department of Chemistry, Merkert Chemistry Center, Boston College , Chestnut Hill, Massachusetts 02467, United States.
Fredrik
F
Haeffner
Department of Chemistry, Merkert Chemistry Center, Boston College , Chestnut Hill, Massachusetts 02467, United States.
Suttipol
S
Radomkit
Department of Chemistry, Merkert Chemistry Center, Boston College , Chestnut Hill, Massachusetts 02467, United States.
Adil R
AR
Zhugralin
Department of Chemistry, Merkert Chemistry Center, Boston College , Chestnut Hill, Massachusetts 02467, United States.
Amir H
AH
Hoveyda
D001895:Boron / Q000737:chemistry*; D002384:Catalysis; D005609:Free Radicals / Q000737:chemistry; D006571:Heterocyclic Compounds / Q000737:chemistry*; D006878:Hydroxides / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*; D007700:Kinetics; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D000432:Methanol / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D010539:Permeability; D012821:Silanes / Q000737:chemistry*; D013237:Stereoisomerism; D014867:Water / Q000737:chemistry
D005609:Free Radicals; D006571:Heterocyclic Compounds; D006878:Hydroxides; D007659:Ketones; D012821:Silanes; D014867:Water; C030011:carbene; D001895:Boron; D008697:Methane; D000432:Methanol