The first chiral diene-based metal-organic frameworks for highly enantioselective carbon-carbon bond formation reactions

Journal Article · Mon Feb 01 04:00:00 EST 2016 · Chemical Science (Online)

DOI:https://doi.org/10.1039/C5SC02100F· OSTI ID:1236871

Sawano, Takahiro; Ji, Pengfei; McIsaac, Alexandra R.; Lin, Zekai; Abney, Carter W.; Lin, Wenbin ^[1]

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1. UC

We have designed the first chiral diene-based metal–organic framework (MOF), E₂-MOF, and postsynthetically metalated E₂-MOF with Rh(I) complexes to afford highly active and enantioselective single-site solid catalysts for C–C bond formation reactions. Treatment of E₂-MOF with [RhCl(C₂H₄)₂]₂ led to a highly enantioselective catalyst for 1,4-additions of arylboronic acids to α,β-unsaturated ketones, whereas treatment of E₂-MOF with Rh(acac)(C₂H₄)₂ afforded a highly efficient catalyst for the asymmetric 1,2-additions of arylboronic acids to aldimines. Interestingly, E₂-MOF·Rh(acac) showed higher activity and enantioselectivity than the homogeneous control catalyst, likely due to the formation of a true single-site catalyst in the MOF. E₂-MOF·Rh(acac) was also successfully recycled and reused at least seven times without loss of yield and enantioselectivity.

• Research Organization: Advanced Photon Source (APS), Argonne National Laboratory (ANL), Argonne, IL (US)
• Sponsoring Organization: NSF
• OSTI ID: 1236871
• Journal Information: Chemical Science (Online), Journal Name: Chemical Science (Online) Journal Issue: (12) ; 2015 Vol. 6; ISSN 2041-6539
• Publisher: Royal Society of Chemistry
• Country of Publication: United States
• Language: ENGLISH