Enantioconvergent and enantiodivergent catalytic hydrogenation of isomeric olefins

Massaro, Luca; Zheng, Jia; Margarita, Cristiana; Andersson, Pher G.

doi:10.1039/c9cs00138g

Cited by 52 publications

(30 citation statements)

References 79 publications

(77 reference statements)

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“…Thus, the enantioselective synthesis of pure aliphatic amines and alcohols has been recognized as a long-term interest in chemistry community. Over the past decades, significant progress has been made in this field enabled by enantioselective C-H amination/ oxygenation [5][6][7][8] , addition of alkyl organometallic reagents to imines or aldehydes [9][10][11][12][13] , and hydrogenation of imines, enamines, ketones, or enol esters [14][15][16][17][18][19] . However, chiral catalysts have difficulty in identifying different faces of prochiral centers bearing two alkyl groups with similar steric and electronic properties 20 .…”

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confidence: 99%

Enantioselective access to chiral aliphatic amines and alcohols via Ni-catalyzed hydroalkylations

Wang

Zhang

et al. 2021

Nat Commun

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Chiral aliphatic amine and alcohol derivatives are ubiquitous in pharmaceuticals, pesticides, natural products and fine chemicals, yet difficult to access due to the challenge to differentiate between the spatially and electronically similar alkyl groups. Herein, we report a nickel-catalyzed enantioselective hydroalkylation of acyl enamines and enol esters with alkyl halides to afford enantioenriched α-branched aliphatic acyl amines and esters in good yields with excellent levels of enantioselectivity. The operationally simple protocol provides a straightforward access to chiral secondary alkyl-substituted amine and secondary alkyl-substituted alcohol derivatives from simple starting materials with great functional group tolerance.

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confidence: 99%

Enantioselective access to chiral aliphatic amines and alcohols via Ni-catalyzed hydroalkylations

Wang

Zhang

et al. 2021

Nat Commun

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“…[1] The scope was further expanded to unfunctionalized, substituted olefins by the Pfaltz group. [2] In parallel, biocatalysts have evolved as valuable tools for asymmetric reactions. [3][4][5] Within this field, oxidoreductases account for over one quarter of the established enzymatic reactions.…”

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confidence: 99%

Enzymatic Asymmetric Reduction of Unfunctionalized C=C Bonds with Archaeal Geranylgeranyl Reductases

et al. 2021

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The asymmetric reduction of activated C=C bonds such as enones is well established for non‐enzymatic methods as well as in biocatalysis. However, the asymmetric reduction of unfunctionalized C=C bonds is mainly performed with transition metal catalysts whereas biocatalytic approaches are lacking. We have tested two FAD‐dependent archaeal geranylgeranyl reductases (GGR) for the asymmetric reduction of isolated C=C bonds. The reduction of up to four double bonds in terpene chains with different chain lengths and head groups was confirmed. Methyl‐branched E ‐alkenes were chemoselectively reduced in the presence of cyclic, terminal or activated alkenes. Using a removable succinate “spacer”, farnesol and geraniol could be quantitatively reduced (>99 %). The reduction is strictly ( R )‐selective (enantiomeric excess >99 %). Hence, GGRs are promising biocatalysts for the asymmetric reduction of unactivated isolated C=C bonds, opening new opportunities for the synthesis of enantiopure branched alkyl chains.

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“…Since AH of C=C bonds without secondary interaction was normally an enantiodivergent process, [ 16 ] we therefore selected…”

Section: Resultsmentioning

confidence: 99%

Enantioselective Hydrogenation of Endocyclic Enones: the Solution to a Historical Problem^†

et al. 2021

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Asymmetric catalysis | Hydrogenation | Cyclic enone | Rhodium | Citral reduction The enantioselective hydrogenation of endocyclic enones has been a historical problem for homogeneous catalysis. We herein report an efficient method to reduce endocyclic enones with molecular hydrogen. Catalyzed by a rhodium/Zhaophos complex, a variety of enones with five-, six-or seven-member ring were hydrogenated with high enantioselectivity (92%-99% ee). Excellent chemo-and enantioselectivity demonstrated this method was successfully applied in the enantioselective hydrogenation of citral to produce enantio-enriched citronellal.

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Enantioconvergent and enantiodivergent catalytic hydrogenation of isomeric olefins

Abstract: In the asymmetric hydrogenation of olefins the enantiodivergent outcome is predominant. However, the less common enantioconvergent phenomenon affords significant practical advantages, such as the possibility to hydrogenate mixtures of E/Z alkenes.

Cited by 52 publications

References 79 publications

Enantioselective access to chiral aliphatic amines and alcohols via Ni-catalyzed hydroalkylations

Enantioselective access to chiral aliphatic amines and alcohols via Ni-catalyzed hydroalkylations

Enzymatic Asymmetric Reduction of Unfunctionalized C=C Bonds with Archaeal Geranylgeranyl Reductases

Enantioselective Hydrogenation of Endocyclic Enones: the Solution to a Historical Problem^†

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Enantioconvergent and enantiodivergent catalytic hydrogenation of isomeric olefins

Abstract: In the asymmetric hydrogenation of olefins the enantiodivergent outcome is predominant. However, the less common enantioconvergent phenomenon affords significant practical advantages, such as the possibility to hydrogenate mixtures of E/Z alkenes.

Cited by 52 publications

References 79 publications

Enantioselective access to chiral aliphatic amines and alcohols via Ni-catalyzed hydroalkylations

Enantioselective access to chiral aliphatic amines and alcohols via Ni-catalyzed hydroalkylations

Enzymatic Asymmetric Reduction of Unfunctionalized C=C Bonds with Archaeal Geranylgeranyl Reductases

Enantioselective Hydrogenation of Endocyclic Enones: the Solution to a Historical Problem†

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Enantioselective Hydrogenation of Endocyclic Enones: the Solution to a Historical Problem^†