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Cited by 138Asymmetric Synthesis and CatalysisChemical Reaction MechanismsMetal-Catalyzed Oxygenation Mechanisms

Mechanistic Basis for High Stereoselectivity and Broad Substrate Scope in the (salen)Co(III)-Catalyzed Hydrolytic Kinetic Resolution

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Ford, David D., Nielsen, Lars P. C., Zuend, Stephan J., Musgrave, Charles B., Jacobsen, Eric N.·2013·Journal of the American Chemical Society
DOI 10.1021/ja408027pPMC PMC3875305
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Abstract

In the (salen)Co(III)-catalyzed hydrolytic kinetic resolution (HKR) of terminal epoxides, the rate- and stereoselectivity-determining epoxide ring-opening step occurs by a cooperative bimetallic mechanism with one Co(III) complex acting as a Lewis acid and another serving to deliver the hydroxide nucleophile. In this paper, we analyze the basis for the extraordinarily high stereoselectivity and broad substrate scope observed in the HKR. We demonstrate that the stereochemistry of each of the two (salen)Co(III) complexes in the rate-determining transition structure is important for productive catalysis: a measurable rate of hydrolysis occurs only if the absolute stereochemistry of each of these (salen)Co(III) complexes is the same. Experimental and computational studies provide strong evidence that stereochemical communication in the HKR is mediated by the stepped conformation of the salen ligand, and not the shape of the chiral diamine backbone of the ligand. A detailed computational analysis reveals that the epoxide binds the Lewis acidic Co(III) complex in a well-defined geometry imposed by stereoelectronic rather than steric effects. This insight serves as the basis of a complete stereochemical and transition structure model that sheds light on the reasons for the broad substrate generality of the HKR.

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  3. [18]For discussions of the step-like conformation of (salen)Mn(V) oxo complexes, see: Cavallo L Jacobsen H Chem. Eur. J 2001 7 800 807 11288871 Katsuki T Adv. Synth. Catal 2002 344 131 147 El-Bahraoui J Wiest O Feichtinger D Plattner DA Angew. Chem., Int. Ed 2001 40 2073 2076 29712213 Cavallo L Jacobsen H J. Org. Chem 2003 68 6202 6207 12895051 For the crystal structure of an achiral, stepped (salen)Cr(V) oxo complex, see: Samsel EG Srinivasan K Kochi JK J. Am. Chem. Soc 1985 107 7606 7617
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  8. [28]For a compilation of crystal structures of (salen)metal complexes, see: Nielsen, L. P. C. Ph. D. Thesis, Harvard University, Cambridge, MA, November, 2006, Appendix 1. The complete text of this document is available via the internet through Proquest (http://www.proquest.com).
  9. [33]Selected examples of the application of B3LYP in quantum chemical calculations of transition metal structure and reactivity Strassner T Taige MA J. Chem. Theory Comput 2005 1 848 855 26641901 Jenkins DM Di Bilio AJ Allen MJ Betley TA Peters JC J. Am. Chem. Soc 2002 124 15336 15350 12487609 Takaoka A Peters JC Inorg. Chem 2012 51 16 18 22133084 Shakya R Imbert C Hratchian HP Lanznaster M Heeg MJ McGarvey BR Allard M Schlegel B Verani CN Dalton Trans 2006 2517 2525 16718335 Araujo CM Doherty MD Konezny SJ Luca OR Usyatinsky A Grade H Lobkovsky E Soloveichik GL Crabtree RH Batista VS Dalton Trans 2012 41 3562 3573 22318461 Wang T Brudvig G Batista VS J. Chem. Theory Comput 2010 6 755 760 20607115 PMC2896228
  10. [41]The kinetic non-lability of six-coodinate Co(III) complexes is well established Crabtree RH The Organometallic Chemistry of the Transition Metals 2005 4th ed. Hoboken John Wiley & Sons 11 12 The effect is illustrated in a dramatic way by the fact that hexaaminecobalt(III) chloride can be purified by recrystallization from concentrated hydrochloric acid in high yield Bjerrum J McReynolds JP Inorg. Synth 1946 2 216 221
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Authors
Ford, D. D., Nielsen, L. P. C., Zuend, S. J., Musgrave, C. B., & Jacobsen, E. N.
Affiliations
  • Harvard University (US)
  • University of Colorado Boulder (US)
Corresponding author
Jacobsen, Eric N.
ORCID
Venue
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Published
2013-10-07
Volume
135
Issue
41
Pages
15595-15608
ISSN
  • 0002-7863 (ISSN-L)
  • 1520-5126
DOI
10.1021/ja408027p
PMC
PMC3875305
OpenAlex
W2131226967
Cited by
138
References
90
Citations by year
2026: 9 · 2025: 8 · 2024: 3 · 2023: 8 · 2022: 11 · 2021: 6 · 2020: 16 · 2019: 10 · 2018: 7 · 2017: 12 · 2016: 16 · 2015: 14 · 2014: 17 · 2013: 1
FWCI
7.29
Type
journal article
Language
en
Open access
Locations
  • Journal of the American Chemical Society (publishedVersion)
  • PubMed (publishedVersion)
  • Europe PMC (PubMed Central) (acceptedVersion)
  • PubMed Central (acceptedVersion)
Funders
National Institute of General Medical Sciences (GM43214, R01GM043214, R37GM043214)
Topics
  • Physical Sciences › Chemistry › Organic Chemistry › Asymmetric Synthesis and Catalysis
  • Physical Sciences › Chemistry › Organic Chemistry › Chemical Reaction Mechanisms
  • Physical Sciences › Chemistry › Inorganic Chemistry › Metal-Catalyzed Oxygenation Mechanisms
Keywords
hydrolytic kinetic resolution, cobalt catalysis, terminal epoxides, epoxide ring opening, stereoselectivity, Lewis acid catalysis, transition state structure, stereoelectronic effects, substrate scope
MeSH terms
Alcohols, Catalysis, Cobalt, Epoxy Compounds, Ethylenediamines, Hydrolysis, Kinetics, Models, Molecular, Organometallic Compounds, Quantum Theory, Stereoisomerism, Molecular Structure

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