2004
DOI: 10.1002/ange.200462432
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Metal‐Free, Organocatalytic Asymmetric Transfer Hydrogenation of α,β‐Unsaturated Aldehydes

Abstract: Asymmetric catalytic hydrogenations are used in the largescale industrial production of pharmaceuticals and fine chemicals and also by all living organisms. While chemical hydrogenations require metal catalysts or the use of stoichiometric amounts of metal hydrides, [1] living organisms typically rely on organic cofactors such as nicotinamide adenine dinucleotide (NADH) in combination with metalloenzymes. [2] Until now, metal-free catalytic asymmetric hydrogenations have been unknown in chemical synthesis an… Show more

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Cited by 124 publications
(59 citation statements)
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“…Whereas cis-hydrogenation using transition metalbased homogeneous catalysts has been developed to an impressive standard, [1] stereocomplementary asymmetric trans-hydrogenation, which resembles the conjugate (Michael-type) addition of a hydride onto a C=C bond bearing an electron-withdrawing substituent is still at the stage of development. [2] The biocatalytic counterpart for the stereoselective reduction of activated alkenes is catalysed by enoate reductases [EC 1.3.1.X], [3][4][5] members of the "old yellow enzyme" family. [6] These enzymes are ubiquitous in nature and their catalytic mechanism has been investigated in great detail (Scheme 1).…”
Section: Introductionmentioning
confidence: 99%
“…Whereas cis-hydrogenation using transition metalbased homogeneous catalysts has been developed to an impressive standard, [1] stereocomplementary asymmetric trans-hydrogenation, which resembles the conjugate (Michael-type) addition of a hydride onto a C=C bond bearing an electron-withdrawing substituent is still at the stage of development. [2] The biocatalytic counterpart for the stereoselective reduction of activated alkenes is catalysed by enoate reductases [EC 1.3.1.X], [3][4][5] members of the "old yellow enzyme" family. [6] These enzymes are ubiquitous in nature and their catalytic mechanism has been investigated in great detail (Scheme 1).…”
Section: Introductionmentioning
confidence: 99%
“…[1] In addition to the well-established transition metal-catalyzed (transfer) hydrogenations [2,3] new methodologies such as organocatalytic [4] or biocatalytic [5] approaches are constantly being added to the toolbox. For the latter, socalled enoate reductases [E.C.…”
Section: Introductionmentioning
confidence: 99%
“…Whereas cis hydrogenation using homogeneous catalysts based on (transition) metals has been developed to a high standard, [1] stereocomplementary trans reduction is still at the stage of development. [2,3] The biocatalytic equivalent of this reaction is catalyzed by enoate reductases [EC 1.3.1.x], [4,5] commonly denoted as the "old yellow enzyme" family.[6] These common enzymes act through transfer of a hydride ion, derived from a flavin cofactor (FMNH 2 ), onto the b-carbon atom of an a,bunsaturated carbonyl compound, while a proton, derived from the solvent, adds from the opposite side onto the acarbon atom. As a consequence of this mechanism, the hydrogenation occurs in a trans-specific fashion.…”
mentioning
confidence: 97%
“…[19] As a result of the presence of multiple C = C and C = O bonds, the asymmetric reduction of citral (1 a, Table 1) in a chemo-, regio-, and stereoselective fashion is a challenging task. [2,20] Both OPR1 and OPR3 quickly reduced the conjugated C=C-bond in a highly chemo-, regio-, and stereoseScheme 1. Asymmetric bioreduction of activated alkenes bearing an activating electron-withdrawing group (EWG) by enoate reductases.…”
mentioning
confidence: 99%