TY - JOUR
T1 - Attractive noncovalent interactions in asymmetric catalysis
T2 - Links between enzymes and small molecule catalysts
AU - Knowles, Robert R.
AU - Jacobsen, Eric N.
N1 - Copyright:
Copyright 2019 Elsevier B.V., All rights reserved.
PY - 2010/11/30
Y1 - 2010/11/30
N2 - Catalysis by neutral, organic, small molecules capable of binding and activating substrates solely via noncovalent interactions-particularly H-bonding-has emerged as an important approach in organocatalysis. The mechanisms by which such small molecule catalysts induce high enantioselectivity may be quite different from those used by catalysts that rely on covalent interactions with substrates. Attractive noncovalent interactions are weaker, less distance dependent, less directional, and more affected by entropy than covalent interactions. However, the conformational constraint required for high stereoinduction may be achieved, in principle, if multiple noncovalent attractive interactions are operating in concert. This perspective will outline some recent efforts to elucidate the cooperative mechanisms responsible for stereoinduction in highly enantioselective reactions promoted by noncovalent catalysts.
AB - Catalysis by neutral, organic, small molecules capable of binding and activating substrates solely via noncovalent interactions-particularly H-bonding-has emerged as an important approach in organocatalysis. The mechanisms by which such small molecule catalysts induce high enantioselectivity may be quite different from those used by catalysts that rely on covalent interactions with substrates. Attractive noncovalent interactions are weaker, less distance dependent, less directional, and more affected by entropy than covalent interactions. However, the conformational constraint required for high stereoinduction may be achieved, in principle, if multiple noncovalent attractive interactions are operating in concert. This perspective will outline some recent efforts to elucidate the cooperative mechanisms responsible for stereoinduction in highly enantioselective reactions promoted by noncovalent catalysts.
KW - Enantioselectivity
KW - H bonding
KW - Organocatalysis
KW - Transition state stabilization
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U2 - 10.1073/pnas.1006402107
DO - 10.1073/pnas.1006402107
M3 - Article
C2 - 20956302
AN - SCOPUS:78650585984
VL - 107
SP - 20678
EP - 20685
JO - Proceedings of the National Academy of Sciences of the United States of America
JF - Proceedings of the National Academy of Sciences of the United States of America
SN - 0027-8424
IS - 48
ER -