Isomerisation of Vinyl Sulfones for the Stereoselective Synthesis of Vinyl Azides

Collins, Niall; Connon, Robert; Sánchez‐Sanz, Goar; Evans, Paul

doi:10.1002/ejoc.202001065

Cited by 10 publications

(3 citation statements)

References 53 publications

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“…[16][17][18][19] Inomata's protocol was subsequently adopted for the total synthesis of the natural products ingenol 20 and avermec n B1a, 21 and has also featured in the synthesis of vinyl azides. 22 Theory supports a thermodynamic preference for the allylic isomer in these systems, explained by the electron-withdrawing nature of sulfoxide and sulfone groups being induc vely unfavorable for a achment to an sp 2 hybridized carbon. 23…”

mentioning

confidence: 67%

Diastereoselective β-Hydroxy Vinylsulfone Isomerizations

O'Neil,

Clark,

Carnahan

et al. 2024

Preprint

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Vinylic phenylsulfones containing a β-hydroxyl stereocenter undergo a diastereoselective isomerization to the corresponding allylic isomer upon treatment with 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU). Diastereoselectivity of this reaction increases with increasing size of the group attached to the carbinol carbon (up to >20:1 d.r. with a tert-butyl). Isolated yields of the isomerized allylic 1,2-hydroxy phenylsulfone products were comparable among the different vinylsulfones tested (59-66%). The major competing pathway was a C-C bond cleavage process, proposed to occur after the initial isomerization event. The sense of diastereoselection was consistent among all substrates investigated, in favor of the erythro-isomer based on NMR analysis.

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mentioning

confidence: 67%

Diastereoselective β-Hydroxy Vinylsulfone Isomerizations

O'Neil,

Clark,

Carnahan

et al. 2024

Preprint

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“…To gain insight into this interplay, geometry optimizations using density functional theory (DFT) have been carried out for compounds 7a – d , 11a–b , 15c , and 17 . To do this, three functionals CAM-B3LYP, WB97XD, and M06-2X were used with def2TZVP as the basis set. − Frequency calculations have been carried out to verify the nature of the minima, and for each compound, true minima have been identified with no imaginary frequencies. According to these calculations, the CAM-B3LYP results most closely match the experimental outcomes (additional data obtained using the other functionals can be found in the Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

Reduction of Substituted Benzo-Fused Cyclic Sulfonamides with Mg-MeOH: An Experimental and Computational Study

et al. 2022

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A study involving the use of Mg-MeOH for the double reductive cleavage of both N–S and C–S bonds in a series of 11 benzo-fused cyclic sulfonamides is reported. Examples where the sulfonamide nitrogen atom is part of a pyrrolidine ring effectively undergo reduction, as long as a methoxy substituent is not para -positioned in the aromatic ring, relative to the sulfonyl group. In contrast, if the nitrogen atom is contained within an aromatic ring (pyrrole or indole), the presence of a para -methoxy substituent does not prohibit reduction. If deuterated methanol is used, aromatic ortho- deuterium incorporation was observed. To better understand how structure affects reactivity, density functional theory calculations were performed using three functionals. Results using CAM-B3LYP were found to best correlate with experimental observations, and these demonstrate the impact that the different aromatic substitution patterns and types of N-atom have on the lowest unoccupied molecular orbital (LUMO) energies and adiabatic electron affinities.

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“…(E)-((4-Methylpent-1-en-1-yl)sulfonyl)benzene (23a). 15 The titled compound 23a was obtained as a colorless oil (49 mg, 72%) according to the GP and purified by silica column chromatography in petroleum ether: ethyl acetate = 4:1. (150 MHz,140.8,133.3,131.3,129.3,127.6,40.6,27.8,22.4.…”

Section: (E)-(oct-1-en-1-yl Sulfonyl)benzene (21a) 14cmentioning

confidence: 99%

Nickel-Catalyzed Direct Sulfonylation of Styrenes and Unactivated Aliphatic Alkenes with Sulfonyl Chlorides

Rao,

Li,

Jiang

et al. 2024

J. Org. Chem.

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A nickel-catalyzed direct sulfonylation of alkenes with sulfonyl chlorides has been developed using 1,10-phenanthroline-5,6-dione as the ligand. Unactivated alkenes and styrenes including 1,1-, 1,2-disubstituted alkenes can be subjected to the protocol, and a wide range of vinyl sulfones was obtained in high to excellent yields with good functional group compatibility. Notably, the process did not allow the desulfonylation of sulfonyl chloride or chlorosulfonylation of alkenes. Radical-trapping experiment supported that a sulfonyl free-radical was likely produced and triggered subsequent transformation in the process.

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Isomerisation of Vinyl Sulfones for the Stereoselective Synthesis of Vinyl Azides

Cited by 10 publications

References 53 publications

Diastereoselective β-Hydroxy Vinylsulfone Isomerizations

Diastereoselective β-Hydroxy Vinylsulfone Isomerizations

Reduction of Substituted Benzo-Fused Cyclic Sulfonamides with Mg-MeOH: An Experimental and Computational Study

Nickel-Catalyzed Direct Sulfonylation of Styrenes and Unactivated Aliphatic Alkenes with Sulfonyl Chlorides

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