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

ABSTRACT: 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 ?,?-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.

SUBMITTER: Sawano T

PROVIDER: S-EPMC5951194 | biostudies-literature | 2015 Dec

REPOSITORIES: biostudies-literature

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

Sawano Takahiro T Ji Pengfei P McIsaac Alexandra R AR Lin Zekai Z Abney Carter W CW Lin Wenbin W

Chemical science 20150914 12

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 E ...[more]

PMID: 29861953

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