Enantioselective Olefin Hydrocyanation without Cyanide

Schuppe, Alexander W.; Borrajo‐Calleja, Gustavo M.; Buchwald, Stephen L.

doi:10.1021/jacs.9b10875

Cited by 51 publications

(25 citation statements)

References 50 publications

(42 reference statements)

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“…Until now, cyanide leaching was widely applied for extracting gold, , which was harmful for the environment owing to the high toxicity of cyanide . As the world advocated and promoted green development, it was urgent to develop an eco-friendly and efficient technique for leaching gold instead of cyanide leaching.…”

Section: Introductionmentioning

confidence: 99%

Efficient Recovery of Gold(I) from Thiosulfate Solutions through Photocatalytic Reduction with Mn(II)-Doped MoS₂

Zhan

Yuan

Yao³

et al. 2021

ACS Sustainable Chem. Eng.

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Developing efficient materials for the extraction of gold(I) was pivotal for application of ammoniacal thiosulfate leaching technology. Mn-doped molybdenum disulfide (Mn-MoS2) spheres were fabricated by a facile hydrothermal route for photocatalytic reduction of the gold(I) thiosulfate complex ([Au(S2O3)2]3–) in this work. The experimental results exhibited that [Au(S2O3)2]3– was efficiently recycled in the form of gold nanoparticles by Mn-MoS2. The reduction capacity (936.9 mg/g) and rate (2.74 mg/(g min) in 300 min) was 1.5 and 2.72 times higher than that of MoS2, respectively. The inside photocatalytic reduction mechanism was studied by combining an experimental and first-principles approach. Outstanding reduction performance of [Au(S2O3)2]3– was attributed to the enhanced transfer of photoinduced electrons after Mn doping. In addition, S atoms in the Mn-S bond could well interact with Au(I), which slightly promoted the adsorption of [Au(S2O3)2]3– on Mn-MoS2. The discovery provided a promising strategy for the efficient extraction of gold(I) from thiosulfate leaching solutions.

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Section: Introductionmentioning

confidence: 99%

Efficient Recovery of Gold(I) from Thiosulfate Solutions through Photocatalytic Reduction with Mn(II)-Doped MoS₂

Zhan

Yuan

Yao³

et al. 2021

ACS Sustainable Chem. Eng.

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“… 11 Following early examples of highly enantioselective hydrocyanation of 2-methoxy-6-vinylnaphthalene by RajanBabu et al in the context of naproxen synthesis, 7 – 9 seminal contributions have been made using transition metal catalysis (e.g., Ni catalysis; Figure 1b ). 12 – 17 To date, however, a general catalytic approach that meets the criteria of both broad reaction scope and high enantioselectivity remains elusive. In particular, internal alkenes, which would lead to a substantially wider range of useful products, have proven to be challenging substrates.…”

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confidence: 99%

Dual electrocatalysis enables enantioselective hydrocyanation of conjugated alkenes

et al. 2020

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Chiral nitriles and their derivatives are prevalent in pharmaceuticals and bioactive compounds. Enantioselective alkene hydrocyanation represents a convenient and efficient approach for synthesizing these molecules. However, a generally applicable method featuring a broad substrate scope and high functional group tolerance remains elusive. Here, we address this long-standing synthetic problem using an electrocatalytic strategy. Electrochemistry allows for the seamless combination of two classic radical reactions-cobalt-mediated hydrogen-atom transfer and copper-promoted radical cyanation-to accomplish highly enantioselective hydrocyanation without the need for stoichiometric oxidant. We harness electrochemistry's unique feature of precise potential control to optimize the chemoselectivity of challenging substrates. Computational analysis sheds light on the origin of enantioinduction, for which the chiral catalyst imparts a combination of attractive and repulsive non-covalent interactions that direct the enantio-determining C-CN bond formation. This discovery demonstrates the power of electrochemistry in accessing new chemical space and providing solutions to pertinent challenges in synthetic chemistry. File list (2) download file view on ChemRxiv 01_Lin_MS.pdf (1.70 MiB) download file view on ChemRxiv 00_Lin_TOC.png (333.52 KiB)

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“…A unique application for the hydrocyanation of olefins employed 2-phenyl-4-methyl-5-bromooxazole 113 as a cyanide equivalent in the enantioselective hydrocyanation of olefins . The initial hydroarylation was Pd-catalyzed, with the asymmetric addition to the olefin promoted by the CuH (Scheme ).…”

Section: Miscellaneous Asymmetric Organosilane Reductionsmentioning

confidence: 76%

Organosilanes in Metal-Catalyzed, Enantioselective Reductions

Larson

Liberatore

2021

Org. Process Res. Dev.

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The growth and development of an extensive range of metals complexed with chiral ligands for the purpose of catalyzing a variety of reactions in an enantioselective manner has been impressive for its scope, chemical yields and high ee values. Chief among the classes of synthetic transformations has been that of the asymmetric reduction of prochiral substrates. These include the asymmetric reduction of prochiral ketones, imines, unsaturated aldehydes, ketones, esters, nitriles and olefins, as well as a number of asymmetric coupling reactions. In concert with these efficient catalyst systems, organosilanes have the ability to carry out any number of organic reductions under a variety of conditions. In these reactions, which in reality are hydrosilylations (hydrosilylation and reduction are considered interchangeable herein) in which the initially resulting silylated product is hydrolyzed to the ultimate desired functionality, the ability to sterically and electronically alter the organosilane reductant can contribute to the overall success of the transformation. In this review, we present a thorough compilation of the literature covering the use of organosilanes in metal-catalyzed asymmetric reductions (hydrosilylations) and coupling reactions.

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Enantioselective Olefin Hydrocyanation without Cyanide

Cited by 51 publications

References 50 publications

Efficient Recovery of Gold(I) from Thiosulfate Solutions through Photocatalytic Reduction with Mn(II)-Doped MoS₂

Efficient Recovery of Gold(I) from Thiosulfate Solutions through Photocatalytic Reduction with Mn(II)-Doped MoS₂

Dual electrocatalysis enables enantioselective hydrocyanation of conjugated alkenes

Organosilanes in Metal-Catalyzed, Enantioselective Reductions

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Enantioselective Olefin Hydrocyanation without Cyanide

Cited by 51 publications

References 50 publications

Efficient Recovery of Gold(I) from Thiosulfate Solutions through Photocatalytic Reduction with Mn(II)-Doped MoS2

Efficient Recovery of Gold(I) from Thiosulfate Solutions through Photocatalytic Reduction with Mn(II)-Doped MoS2

Dual electrocatalysis enables enantioselective hydrocyanation of conjugated alkenes

Organosilanes in Metal-Catalyzed, Enantioselective Reductions

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Efficient Recovery of Gold(I) from Thiosulfate Solutions through Photocatalytic Reduction with Mn(II)-Doped MoS₂

Efficient Recovery of Gold(I) from Thiosulfate Solutions through Photocatalytic Reduction with Mn(II)-Doped MoS₂