Thiourea-Mediated Stereospecific Deoxygenation of Cyanoepoxides to Access Highly Diastereopure Alkenyl Nitriles

Zhang, Yujie; Shi, Shukui; Yang, Zhanhui

doi:10.1021/acs.joc.3c02869

Cited by 2 publications

(1 citation statement)

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“…Furthermore, we demonstrated the applicability of our method for the stereoselective synthesis of pyrrolidine derivatives, which are valuable compounds in organic synthesis . The synthesis of cis - and trans -3,4-substituted pyrrolidine 5 was successfully achieved by utilizing both isomers of 3a and an in situ-generated azomethine ylide via [3 + 2]-cycloaddition (Scheme A-2) . Owing to the challenges in synthesizing ( Z )-vinyl sulfones, there have been few reported synthetic applications utilizing them.…”

Section: Resultsmentioning

confidence: 99%

Hydrosulfonylation of Alkynes for Stereodivergent Synthesis of Vinyl Sulfones: Synthetic Strategy and Mechanistic Insights

K P,

Russelisaac Premakumari,

Cho

et al. 2024

J. Am. Chem. Soc.

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Direct synthesis of thermodynamically less favorable (Z)-vinyl sulfones presents a notable challenge in organic synthesis. In addition, the development of a stereodivergent synthesis for (E)-and (Z)-vinyl sulfones is crucial but remains elusive. In this study, we present a hydrosulfonylation of aryl-substituted alkynes, achieving a stereodivergent synthesis of (E)-and (Z)-vinyl sulfones by leveraging both thermodynamic and kinetic controls. Notably, the synthesis of challenging (Z)-vinyl sulfones was achieved through a kinetically controlled process without the need for a catalyst. To synthesize (E)vinyl sulfones, unconventional visible light-mediated isomerization was employed as a means of facilitating the transition to the thermodynamically favored form. The present study encompasses a comprehensive experimental and computational investigation, which provides valuable insights into the reaction mechanism. This investigation reveals two plausible isomerization pathways: a novel double spin-flip mechanism and a hydrogen atom transfer process in the presence of eosin Y. This study not only advances our understanding of isomerization mechanisms beyond conventional energy-transfer routes but also offers a robust and switchable strategy for synthesizing (E)-and (Z)-vinyl sulfones, thereby providing a versatile avenue for the creation of valuable compounds in the fields of organic synthesis and medicinal chemistry.

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Section: Resultsmentioning

confidence: 99%

Hydrosulfonylation of Alkynes for Stereodivergent Synthesis of Vinyl Sulfones: Synthetic Strategy and Mechanistic Insights

K P,

Russelisaac Premakumari,

Cho

et al. 2024

J. Am. Chem. Soc.

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Recent Advances in π-Stacking Interaction-Controlled Asymmetric Synthesis

2024

Molecules

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The π-stacking interaction is one of the most important intramolecular and intermolecular noncovalent interactions in organic chemistry. It plays an important role in stabilizing some structures and transition states in certain reactions via both intramolecular and intermolecular interactions, facilitating different selectivities, such as chemo-, regio-, and stereoselectivities. This minireview focuses on the recent examples of the π-stacking interaction-controlled asymmetric synthesis, including auxiliary-induced asymmetric synthesis, kinetic resolution, asymmetric synthesis of helicenes and heterohelicenes, and multilayer 3D chiral molecules.

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Thiourea-Mediated Stereospecific Deoxygenation of Cyanoepoxides to Access Highly Diastereopure Alkenyl Nitriles

Abstract: A practical and efficient protocol for synthesis of >99% diastereopure Z-and E-alkenyl nitriles is developed, through tetramethylthiourea-mediated stereospecific deoxygenation of respective cis-and transcyanoepoxides in ethanol. The desired products are obtained in excellent yields.

Cited by 2 publications

References 77 publications

Hydrosulfonylation of Alkynes for Stereodivergent Synthesis of Vinyl Sulfones: Synthetic Strategy and Mechanistic Insights

Hydrosulfonylation of Alkynes for Stereodivergent Synthesis of Vinyl Sulfones: Synthetic Strategy and Mechanistic Insights

Recent Advances in π-Stacking Interaction-Controlled Asymmetric Synthesis

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