Photo‐biocatalytic One‐Pot Cascades for the Enantioselective Synthesis of 1,3‐Mercaptoalkanol Volatile Sulfur Compounds

Lauder, Kate; Toscani, Anita; Qi, Yuyin; Lim, Jesmine; Charnock, Simon J.; Korah, Krupa; Castagnolo, Daniele

doi:10.1002/anie.201802135

Cited by 76 publications

(45 citation statements)

References 28 publications

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“…Castagnolo and coworkers very recently reported highly enantioselective one‐pot two‐step photo‐biocatalytic cascade protocol for the synthesis of 1,3‐mercapto alkanols 167 from α,β‐unsaturated ketones 165 and thiols 166 (Scheme ) . This procedure progressed in two steps, the first step proceeded via anti‐Markovnikov thiol‐ene reaction, whereas in second ketoreductase (KRED) biocatalysts provided the enantioselective product 167 with opposite enantioselectivity and thus this protocols are effective for a wide range of substrates.…”

Section: Synthetic Methods For Anti‐markovnikov Thiol‐ene Reactionmentioning

confidence: 99%

Thiol−Ene Reaction: Synthetic Aspects and Mechanistic Studies of an Anti‐Markovnikov‐Selective Hydrothiolation of Olefins

2018

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In synthetic organic chemistry, the anti-Markovnikov thiolÀ ene click (TEC) reaction has emerged as a powerful and widely used approach to build carbonÀ sulfur (CÀ S) bonds owing to several inherent benefits, including simple synthetic procedures, high atom economy with no side products, and easy purification, which results in the formation of linear thioethers in high yield under mild reaction conditions. These TEC reactions have numerous trapping applications in the field of nanoengineering, polymer science, and in medicinal chemistry for the synthesis of many drugs and bioactive molecules. This present review highlights the diversity of TEC reaction in terms of substrates, catalysts and mechanistic studies towards the generation of highly selective anti-Markovnikov adduct under metal-free, metalcatalyzed, and photo-induced reaction conditions.

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Section: Synthetic Methods For Anti‐markovnikov Thiol‐ene Reactionmentioning

confidence: 99%

Thiol−Ene Reaction: Synthetic Aspects and Mechanistic Studies of an Anti‐Markovnikov‐Selective Hydrothiolation of Olefins

2018

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“…One example of such light‐triggered substrate functionalization combined with an enzymatic transformation was provided by Castagnolo et al. Here, the photothiolation of α,β‐unsaturated ketones 75 with subsequent asymmetric reduction (Table ) was demonstrated . Irradiation of 75 with visible light in the presence of 0.3 mol % Ru(bpy) 3 Cl 2 and a thiol furnished the ketones 76 , and these served as excellent substrates for enzymatic reduction.…”

Section: Photo‐biocatalysis By Application Of Isolated Enzymes or Celmentioning

confidence: 99%

Biocatalysis Fueled by Light: On the Versatile Combination of Photocatalysis and Enzymes

Seel

Gulder

2019

ChemBioChem

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Enzymes catalyze a plethora of highly specific transformations under mild and environmentally benign reaction conditions. Their fascinating performances attest to high synthetic potential that is often hampered by operational obstacles such as in vitro cofactor supply and regeneration. Exploiting light and combining it with biocatalysis not only helps in overcoming these drawbacks, but the fruitful liaison of these two fields of “green chemistry” also offers opportunities to unlock new synthetic reactivities. In this review we provide an overview of the wide variety of photo‐biocatalysis, ranging from the photochemical delivery of electrons required in redox biocatalysis and photochemical cofactor and reagent (re)generation to direct photoactivation of enzymes enabling reactions unknown in nature. We highlight synthetically relevant transformations such as asymmetric reactions facilitated by the combination of light as energy source and enzymes’ catalytic power.

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“…Due to our interest in the development of green and sustainable biocatalytic methodologies to access VSC and drug‐like compounds, herein we describe a DKR approach to synthesise enantiomerically pure α‐thiocarboxylic acids from racemic α‐thionitriles exploiting nitrilase enzymes. Nitrilases catalyse the hydrolysis of nitriles into the corresponding carboxylic acids with the formation of ammonia as side product.…”

Section: Figurementioning

confidence: 99%

Enantioselective Synthesis of α‐Thiocarboxylic Acids by Nitrilase Biocatalysed Dynamic Kinetic Resolution of α‐Thionitriles

Lauder

Anselmi

Finnigan

et al. 2020

Chemistry A European J

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The enantioselective synthesis of α‐thiocarboxylic acids by biocatalytic dynamic kinetic resolution (DKR) of nitrile precursors exploiting nitrilase enzymes is described. A panel of 35 nitrilase biocatalysts were screened and enzymes Nit27 and Nit34 were found to catalyse the DKR of racemic α‐thionitriles under mild conditions, affording the corresponding carboxylic acids with high conversions and good‐to‐excellent ee. The ammonia produced in situ during the biocatalytic transformation favours the racemization of the nitrile enantiomers and, in turn, the DKR without the need of any external additive base.

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Photo‐biocatalytic One‐Pot Cascades for the Enantioselective Synthesis of 1,3‐Mercaptoalkanol Volatile Sulfur Compounds

Cited by 76 publications

References 28 publications

Thiol−Ene Reaction: Synthetic Aspects and Mechanistic Studies of an Anti‐Markovnikov‐Selective Hydrothiolation of Olefins

Thiol−Ene Reaction: Synthetic Aspects and Mechanistic Studies of an Anti‐Markovnikov‐Selective Hydrothiolation of Olefins

Biocatalysis Fueled by Light: On the Versatile Combination of Photocatalysis and Enzymes

Enantioselective Synthesis of α‐Thiocarboxylic Acids by Nitrilase Biocatalysed Dynamic Kinetic Resolution of α‐Thionitriles

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