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Enantioselective hydroformylation by a Rh-catalyst entrapped in a supramolecular metallocage

Regio- and enantioselective hydroformylation of styrenes is attained upon embedding a chiral Rh complex in a nonchiral supramolecular cage formed from coordination-driven self-assembly of macrocyclic dipalladium complexes and tetracarboxylate zinc porphyrins. The resulting supramolecular catalyst converts styrene derivatives into aldehyde products with much higher chiral induction in comparison to the nonencapsulated Rh catalyst. Spectroscopic analysis shows that encapsulation does not change the electronic properties of the catalyst nor its first coordination sphere. Instead, enhanced enantioselectivity is rationalized by the modification of the second coordination sphere occurring upon catalyst inclusion inside the cage, being one of the few examples in achieving an enantioselective outcome via indirect through-space control of the chirality around the catalyst center. This effect resembles those taking place in enzymatic sites, where structural constraints imposed by the enzyme cavity can impart stereoselectivities that cannot be attained in bulk. These results are a showcase for the future development of asymmetric catalysis by using size-tunable supramolecular capsules

We thank the European Research Council (ERC-2011-StG- 277801 to X.R., ERC-2009-StG-239910 to M.C., and ERC- 2013-AdG-339782-NAT_CAT to J.N.H.R.), the Spanish MINECO (Consolider-Ingenio CSD2010-00065, INNPLANTA project INP-2011-0059-PCT-420000-ACT1, and CTQ2012-32436), and the Catalan DIUE of the Generalitat de Catalunya (2009SGR637 and PhD grant to C.G.S.)

© Journal of the American Chemical Society, 2015, vol. 137, p. 2680-2687

American Chemical Society (ACS)

Author: García Simón, Cristina
Gramage Doria, Rafael
Raoufmoghaddam, Saeed
Parella Coll, Teodor
Costas Salgueiro, Miquel
Ribas Salamaña, Xavi
Reek, Joost N.H.
Date: 2015
Abstract: Regio- and enantioselective hydroformylation of styrenes is attained upon embedding a chiral Rh complex in a nonchiral supramolecular cage formed from coordination-driven self-assembly of macrocyclic dipalladium complexes and tetracarboxylate zinc porphyrins. The resulting supramolecular catalyst converts styrene derivatives into aldehyde products with much higher chiral induction in comparison to the nonencapsulated Rh catalyst. Spectroscopic analysis shows that encapsulation does not change the electronic properties of the catalyst nor its first coordination sphere. Instead, enhanced enantioselectivity is rationalized by the modification of the second coordination sphere occurring upon catalyst inclusion inside the cage, being one of the few examples in achieving an enantioselective outcome via indirect through-space control of the chirality around the catalyst center. This effect resembles those taking place in enzymatic sites, where structural constraints imposed by the enzyme cavity can impart stereoselectivities that cannot be attained in bulk. These results are a showcase for the future development of asymmetric catalysis by using size-tunable supramolecular capsules
We thank the European Research Council (ERC-2011-StG- 277801 to X.R., ERC-2009-StG-239910 to M.C., and ERC- 2013-AdG-339782-NAT_CAT to J.N.H.R.), the Spanish MINECO (Consolider-Ingenio CSD2010-00065, INNPLANTA project INP-2011-0059-PCT-420000-ACT1, and CTQ2012-32436), and the Catalan DIUE of the Generalitat de Catalunya (2009SGR637 and PhD grant to C.G.S.)
Format: application/pdf
ISSN: 0002-7863 (versió paper)
1520-5126 (versió electrònica)
Document access: http://hdl.handle.net/10256/12117
Language: eng
Publisher: American Chemical Society (ACS)
Collection: MICINN/PN 2010-2016/CSD2010-00065
MICINN/PN 2011/INP-2011-0059-PCT-420000
AGAUR/2009-2014/2009 SGR-637
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/ja512637k
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/277801
info:eu-repo/grantAgreement/EC/FP7/239910
Is part of: © Journal of the American Chemical Society, 2015, vol. 137, p. 2680-2687
Rights: Tots els drets reservats
Subject: Catalitzadors de rodi
Rhodium catalyst
Title: Enantioselective hydroformylation by a Rh-catalyst entrapped in a supramolecular metallocage
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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