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Title: 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 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.

Authors:
; ; ; ; ;  [1]
  1. UC
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
National Science Foundation (NSF)
OSTI Identifier:
1236871
Resource Type:
Journal Article
Journal Name:
Chemical Science (Online)
Additional Journal Information:
Journal Volume: 6; Journal Issue: (12) ; 2015; Journal ID: ISSN 2041-6539
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Sawano, Takahiro, Ji, Pengfei, McIsaac, Alexandra R., Lin, Zekai, Abney, Carter W., and Lin, Wenbin. The first chiral diene-based metal-organic frameworks for highly enantioselective carbon-carbon bond formation reactions. United States: N. p., 2016. Web. doi:10.1039/C5SC02100F.
Sawano, Takahiro, Ji, Pengfei, McIsaac, Alexandra R., Lin, Zekai, Abney, Carter W., & Lin, Wenbin. The first chiral diene-based metal-organic frameworks for highly enantioselective carbon-carbon bond formation reactions. United States. doi:10.1039/C5SC02100F.
Sawano, Takahiro, Ji, Pengfei, McIsaac, Alexandra R., Lin, Zekai, Abney, Carter W., and Lin, Wenbin. Mon . "The first chiral diene-based metal-organic frameworks for highly enantioselective carbon-carbon bond formation reactions". United States. doi:10.1039/C5SC02100F.
@article{osti_1236871,
title = {The first chiral diene-based metal-organic frameworks for highly enantioselective carbon-carbon bond formation reactions},
author = {Sawano, Takahiro and Ji, Pengfei and McIsaac, Alexandra R. and Lin, Zekai and Abney, Carter W. and Lin, Wenbin},
abstractNote = {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.},
doi = {10.1039/C5SC02100F},
journal = {Chemical Science (Online)},
issn = {2041-6539},
number = (12) ; 2015,
volume = 6,
place = {United States},
year = {2016},
month = {2}
}