Regio- and stereoselective manganese-catalyzed hydrosulfonylation of alkynes: facile access to <i>Z</i>-vinyl sulfones

Han, Jian; Zeng, Li-Li; Huang, Rong-Hui; Feng, Xiao-Qing; Chen, Fen-Er

doi:10.1039/d3qo01187a

Cited by 3 publications

(1 citation statement)

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“…The reaction yield and selectivity were moderate in this study (1 example, 42% yield, Z / E = 7/1). Recently, Han and Chen reported a manganese-catalyzed synthesis of ( Z )-vinyl sulfones using alkyl- or aryl-substituted alkynes through hydrosulfonylation . In this study, the selectivity with aryl-substituted alkynes was low to moderate, and the substrate scope was limited (11 examples, Z : E ≥ 1:1).…”

Section: Introductionmentioning

confidence: 92%

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: Introductionmentioning

confidence: 92%

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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Blue‐Light Irradiated Mn(0)‐Catalyzed Hydroxylation and C(sp³)−H Functionalization of Unactivated Alkanes with C(sp²)−H Bonds of Quinones for Alkylated Hydroxy Quinones and Parvaquone

Kumar Jha,

Rohilla,

Jain

et al. 2024

Chemistry A European J

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Site‐selective C(sp3)‐H functionalization of unreactive hydrocarbons is always challenging due to its inherited chemical inertness, slightly different reactivity of various C‐H bonds, and intrinsically high bond dissociation energies. Here, we present a site‐selective C−H alkylation of naphthoquinone with unactivated hydrocarbons using Mn2(CO)10 as a catalyst under blue‐light (457 nm) irradiation without any external acid or base and pre‐functionalization. The selective C‐H functionalization of tertiary over secondary and secondary over primary C(sp3)−H bonds in abundant chemical feedstocks was achieved, and hydroxylation of quinones was realized in situ by employing the developed methodology. This protocol provides a new catalytic system for the direct construction of high‐value‐added compounds, namely, parvaquone (a commercially available drug, used to treat theileriosis) and its derivatives under ambient reaction conditions. Moreover, this operationally simple protocol applies to various linear‐, branched‐, and cyclo‐alkanes with high degrees of site selectivity under blue‐light conditions and could provide rapid and straightforward access to versatile methodologies for upgrading feedstock chemicals. Mechanistic insight by radical trapping, radical scavenging, EPR, and other controlled experiments well corroborated with DFT studies suggest that the reaction proceeds by a radical pathway.

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Photochemical Halogen-Bonding Promoted Synthesis of Vinyl Sulfones via Vinyl and Sulfonyl Radicals

Jiang,

You,

et al. 2024

Org. Lett.

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A photochemical halogen-bonding-assisted synthesis of vinyl sulfones via radical−radical cross-coupling of vinyl bromines and sodium sulfinates is developed. This methodology offers a facile and efficient approach to various vinyl sulfones with excellent functional group tolerance under metal-, photocatalyst-, base-, and oxidant-free conditions. The reaction is also applicable for the late-stage functionalization of drug molecules and the hectogram scale. Moreover, instead of sodium sulfites being prepared, these reactions could also be conducted using sulfonyl chlorides in a one-pot method.

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Regio- and stereoselective manganese-catalyzed hydrosulfonylation of alkynes: facile access to Z-vinyl sulfones

Abstract: A concise and practical route for manganese-catalyzed hydrosulfonylation of alkynes with commercially and easily available sulfonyl chlorides has been reported. This protocol features mild conditions, convenient operation and good functional...

Cited by 3 publications

References 70 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

Blue‐Light Irradiated Mn(0)‐Catalyzed Hydroxylation and C(sp³)−H Functionalization of Unactivated Alkanes with C(sp²)−H Bonds of Quinones for Alkylated Hydroxy Quinones and Parvaquone

Photochemical Halogen-Bonding Promoted Synthesis of Vinyl Sulfones via Vinyl and Sulfonyl Radicals

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Regio- and stereoselective manganese-catalyzed hydrosulfonylation of alkynes: facile access to Z-vinyl sulfones

Abstract: A concise and practical route for manganese-catalyzed hydrosulfonylation of alkynes with commercially and easily available sulfonyl chlorides has been reported. This protocol features mild conditions, convenient operation and good functional...

Cited by 3 publications

References 70 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

Blue‐Light Irradiated Mn(0)‐Catalyzed Hydroxylation and C(sp3)−H Functionalization of Unactivated Alkanes with C(sp2)−H Bonds of Quinones for Alkylated Hydroxy Quinones and Parvaquone

Photochemical Halogen-Bonding Promoted Synthesis of Vinyl Sulfones via Vinyl and Sulfonyl Radicals

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Blue‐Light Irradiated Mn(0)‐Catalyzed Hydroxylation and C(sp³)−H Functionalization of Unactivated Alkanes with C(sp²)−H Bonds of Quinones for Alkylated Hydroxy Quinones and Parvaquone