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New Chiral Molybdenum Catalysts for Asymmetric Olefin Metathesis that Contain 3,3‘-Disubstituted Octahydrobinaphtholate or 2,6-Dichlorophenylimido Ligands

Supporting Info

Richard R. Schrock,*^† Jennifer Y. Jamieson,^† Sarah J. Dolman,^† Stephen A. Miller,^† Peter J. Bonitatebus, Jr.,^† and Amir H. Hoveyda^‡

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, and Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467

Organometallics, 2002, 21 (2), pp 409–417

DOI: 10.1021/om0107441

Publication Date (Web): December 19, 2001

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

†

Massachusetts Institute of Technology.

‡

Merkert Chemistry Center, Boston College.

Abstract

Optically pure (R)-5,5‘,6,6‘,7,7‘,8,8‘-octahydro-1,1‘-bi-2-naphthol was derivatized with mesityl and benzhydryl groups in the 3 and 3‘ positions to give R-H₂Mes₂Bitet and R-H₂Benz₂Bitet, respectively. Addition of R-K₂Benz₂Bitet to Mo(NAr)(CHCMe₂Ph)(OTf)₂(dme) yielded Mo(NAr)(CHCMe₂Ph)(R-Benz₂Bitet)(THF) (7), while addition of R-K₂Mes₂Bitet to Mo(NAr)(CHCMe₂Ph)(OTf)₂(dme) in THF gave Mo(NAr)(CHCMe₂Ph)(R-Mes₂Bitet)(THF) (8). Four complexes that contained the 2,6-dichlorophenylimido ligand were prepared by similar procedures, namely, Mo(NAr_Cl)(CHCMe₃)(S-Biphen)(THF) (9), Mo(NAr_Cl)(CHCMe₃)(R-Trip₂BINO)(THF) (10), Mo(NAr_Cl)(CHCMe₃)(R-Mes₂Bitet)(THF) (11), and Mo(NAr_Cl)(CHCMe₃)(R-Benz₂Bitet)(THF) (12). X-ray studies of 8, 9, and 12 revealed them to be typical distorted trigonal bipyramids with THF and one biphenolate oxygen occupying axial positions. In 9 and 12 the alkylidene orientation was found to be syn, while in 8 the alkylidene orientation was found to be anti. Catalysts 7, 8, 9, 10, 11, and 12 were all efficient in terms of both conversion and % ee for two standard desymmetrization reactions to form dihydrofurans.

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Published In Issue January 21, 2002
Received August 14, 2001

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Article

New Chiral Molybdenum Catalysts for Asymmetric Olefin Metathesis that Contain 3,3‘-Disubstituted Octahydrobinaphtholate or 2,6-Dichlorophenylimido Ligands

Abstract

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