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. 2015 Dec 1;6(12):7163-7168.
doi: 10.1039/c5sc02100f. Epub 2015 Sep 14.

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

Takahiro Sawano  1 , Pengfei Ji  1 , Alexandra R McIsaac  1 , Zekai Lin  1 , Carter W Abney  1 , Wenbin Lin  1
Affiliations

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

Takahiro Sawano et al. Chem Sci. .

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.

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Figures

Fig. 1
Fig. 1. Postsynthetically Rh-metalated E2-MOF catalysts for asymmetric reactions.
Scheme 1
Scheme 1. Synthesis of LH2. (i) oxalyl chloride, CH2Cl2; (ii) TEA, THF, 57% yield over 2 steps; (iii) NaOH, THF, EtOH, 77% yield; (iv) ZrCl4, TFA, DMF, 70 °C, 5 d, 42% yield.
Fig. 2
Fig. 2. (a) PXRD patterns of pristine E2-MOF (simulated from the CIF file, black; experimental, red), and freshly prepared E2-MOF·RhCl (blue) and E2-MOF·Rh(acac) (pink). (b) PXRD patterns of pristine E2-MOF·Rh(acac) (black) and E2-MOF·Rh(acac) recovered from 1,2-addition reactions (after 1st run (red) and 8th run (blue)). (c) EXAFS data (squares) and best fits(lines) for E2-MOF·RhCl. Data are displayed in R-space containing both magnitude of Fourier transform and real components. An R-factor of 0.01 was obtained for the fit. (d) A comparison of EXAFS data for E2-MOF·RhCl, RhCl(LMe2), and the [RhCl(nbd)]2 dimer. (e) EXAFS data (squares) and best fits (lines) for E2-MOF·Rh(acac). An R-factor of 0.016 was obtained for the fit. (f) A comparison of EXAFS data for E2-MOF·Rh(acac) and Rh(acac)-LMe2.
Fig. 3
Fig. 3. (a) Structures of rhodium-coordinated diene complexes in MOF catalyst and the homogeneous control catalyst. (b) Plot of yield (%) and ee (%) of 1,2-addition product at various runs in the recycle and reuse of E2-MOF·Rh(acac) (6 mol% Rh) for 1,2-addition of aldimine 4a with phenylboronic acid (2a).
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