Monodentate non-C(2)-symmetric chiral N-heterocyclic carbene complexes for enantioselective synthesis. Cu-catalyzed conjugate additions of aryl- and alkenylsilylfluorides to cyclic enones.
A new class of enantioselective conjugate addition (ECA) reactions that involve aryl- or alkenylsilyl fluoride reagents and are catalyzed by chiral non-C(2)-symmetric Cu-based N-heterocyclic carbene (NHC) complexes are disclosed. Transformations have been designed based on the principle that a catalytically active chiral NHC-Cu-aryl or NHC-Cu-alkenyl complex can be accessed from reaction of a Cu-halide precursor with in situ-generated aryl- or alkenyltetrafluorosilicate. Reactions proceed in the presence of 1.5 equiv of the aryl- or alkenylsilane reagents and 1.5 equiv of tris(dimethylamino)sulfonium difluorotrimethylsilicate (TASF). Desired products are isolated in 63-97% yield and 73.5:26.5-98.5:1.5 enantiomeric ratio (47%-97% ee). A major focus of the present studies is the design, evaluation, and development of new chiral imidazolinium salts and their derived NHC-Cu complexes as catalysts that promote reactions of various carbosilanes to a range of electrophilic substrates. Toward this end, nearly 20 new chiral monodentate imidazolinium salts, most of which are non-C(2)-symmetric, have been prepared and fully characterized and their ability to serve as catalysts in the ECA reactions has been investigated.
Lee
Kang-sang
KS
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
Hoveyda
Amir H
AH
D000475:Alkenes / Q000138:chemical synthesis*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D003516:Cycloparaffins / Q000737:chemistry*; D003517:Cyclopentanes / Q000138:chemical synthesis*; D005459:Fluorides / Q000737:chemistry; D006573:Heterocyclic Compounds, 1-Ring / Q000737:chemistry; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry; D013237:Stereoisomerism
D000475:Alkenes; D003516:Cycloparaffins; D003517:Cyclopentanes; D006573:Heterocyclic Compounds, 1-Ring; D007659:Ketones; D009942:Organometallic Compounds; C007201:cyclopentanone; C030011:carbene; D003300:Copper; D008697:Methane; D005459:Fluorides