Peptide‐Catalyzed Regio‐ and Enantioselective Reduction of α,β,γ,δ‐Unsaturated Aldehydes

Akagawa, Kengo; Sen, Jun; Kudo, Kazuaki

doi:10.1002/anie.201305004

Cited by 43 publications

(18 citation statements)

References 80 publications

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“…1,6-additions to α,β,γ,δ-diunsaturated aldehydes are challenging and especially thiol additions and Hantzsch ester mediated reductions are known to proceed with low selectivity to provide a mixture of products. 37 , 38 …”

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confidence: 99%

Stable gold(III) catalysts by oxidative addition of a carbon–carbon bond

Horibe

Jacobsen

et al. 2015

Nature

265

193

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Whereas low-valent late transition metal catalysis has become indispensible for chemical synthesis, homogeneous high-valent transition metal catalysis is underdeveloped, mainly due to the reactivity of high-valent transition metal complexes and the challenges associated with synthesizing them. In this manuscript, we report a mild carbon-carbon bond cleavage reaction by a Au(I) complex that generates a stable Au(III) cationic complex. Complementary to the well-established soft and carbophilic Au(I) catalyst, this Au(III) complex exhibits hard, oxophilic Lewis acidity. This is exemplified by catalytic activation of α,β-unsaturated aldehydes towards selective conjugate additions as well as activation of an unsaturated aldehyde-allene for a [2 + 2] cycloaddition reaction. The origin of the regioselectivity and catalytic activity was elucidated by X-ray crystallographic analysis of an isolated Au(III)-activated cinnamaldehyde intermediate. The concepts revealed in this study provide a strategy for accessing high-valent transition metal catalysis from readily available precursors.

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confidence: 99%

Stable gold(III) catalysts by oxidative addition of a carbon–carbon bond

Horibe

Jacobsen

et al. 2015

Nature

265

193

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“…2 a could be easily derivatized to phenoxanol which is a rose fragrance widely used in fragrance compound and household toiletries (Scheme 3). [16] …”

Section: Resultsmentioning

confidence: 99%

Cobalt‐Catalyzed Asymmetric 1,4‐Reduction of β,β‐Dialkyl α,β‐Unsaturated Esters with PMHS

2021

Eur J Org Chem

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A cobalt‐catalyzed asymmetric reduction of β,β‐dialkyl α,β‐unsaturated esters with polymethylhydrosiloxane (PMHS) was reported to deliver the corresponding esters containing a chiral trialkyl carbon center at β‐position with up to 97 % yield and 98 % ee. The chiral tridentate ligand oxazoline iminopyridine (OIP) could perform well for the asymmetric reduction instead of chiral bidentate ligands. This operationally simple protocol shows a broad scope of substrates using one equivalent of readily available PMHS as a cheap and easy‐to‐handle reductive reagent.

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“…By using the peptide polymer 41, in combination with 42, a highly regio-and enantioselective reduction of a,b,g,d-unsaturated aldehyde 43 to afford 44 and 45 was achieved (Scheme 12). 28 The most reactive peptidic organocatalysts developed to date for the aldol 29 and Michael addition 30,31 reactions were reported by Wennemers et al A continuous ow process was also developed by using the polymer-immobilized Wennemers' tripeptide 46 for the synthesis of 47 (Scheme 13). 32 2.1.4 Immobilized chiral imidazolidinone (MacMillan) catalysts.…”

Section: Polymer-immobilized Chiral Organocatalystsmentioning

confidence: 99%

Polymer-immobilized chiral catalysts

Itsuno

Hassan

2014

RSC Adv.

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This review illustrates the current strategies and potential of polymer-immobilized chiral catalysts for highly enantioselective asymmetric synthesis. Abstract:Polymer immobilization of chiral catalysts has progressed extensively over the past years. Recent intensive development of chiral organocatalysts resulted in the identification of numerous highly active catalysts, which are, however, still far less effective than transition metal catalysts. Separation of relatively large amounts of organocatalysts from the reaction mixture causes problems during product isolation. In the case of chirally modified metal catalysts, recovery of the valuable metal species and suppression of metal leaching are perpetually important requirements in the design of environmentally friendly chemical processes. Various types of chiral organocatalysts and metal catalysts have been immobilized as pendant groups onto the side chains of polymer supports. Another important polymer immobilization technique is the incorporation of a chiral catalyst into its main chain, with several types of chiral catalyst monomers having been copolymerized with achiral monomers for their production.Recently, the synthesis of chiral main-chain polymeric catalysts has progressed extensively. Moreover, many examples of polymer-immobilized catalysts exhibited higher enantioselectivities in comparison to those of the corresponding low-molecular-weight catalyst. The development of these polymer-immobilized chiral

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Peptide‐Catalyzed Regio‐ and Enantioselective Reduction of α,β,γ,δ‐Unsaturated Aldehydes

Cited by 43 publications

References 80 publications

Stable gold(III) catalysts by oxidative addition of a carbon–carbon bond

Stable gold(III) catalysts by oxidative addition of a carbon–carbon bond

Cobalt‐Catalyzed Asymmetric 1,4‐Reduction of β,β‐Dialkyl α,β‐Unsaturated Esters with PMHS

Polymer-immobilized chiral catalysts

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