Rhodium‐Catalyzed Alkyne Hydrothiolation with Aromatic and Aliphatic Thiols.

Cao, Changsheng; Fraser, Lauren R.; Love, Jennifer A.

doi:10.1002/chin.200616093

Cited by 3 publications

(3 citation statements)

References 2 publications

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“…We anticipated that direct oxidation/imidation of vinyl thioethers (1.3 equiv) tBuOK would be the most direct path. A range of metal-catalysed alkyne hydrothiolation reactions have been developed that facilitate the synthesis of either branched, 36,37 linear E-vinyl thioethers 38 or linear Z-vinyl thioethers 39 in high selectivity. For this study we were interested in linear E-vinyl sulfoximines and applied a Wilkinson's catalyst mediated alkyne thiolalkyation methodology reported by Love which gives high levels of stereocontrol using 1,2-dichloroethane (DCE) as solvent.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Configurational Assignment of Vinyl Sulfoximines and Sulfonimidamides

Craven¹,

Briggs²,

Zammit³

et al. 2021

Preprint

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Vinyl sulfones and sulfonamides are valued for their use as electrophilic warheads in covalent protein inhibitors. Conversely, the S(VI) aza-isosteres thereof, vinyl sulfoximines and sulfonimidamides, are far less studied and have yet to be applied to the field of protein bioconjugation. Herein, we report a range of different synthetic methodologies for constructing vinyl sulfoximine and vinyl sulfonimidamide architectures that allows access to new areas of electrophilic chemical space. We demonstrate how late stage functionalization can be applied to these motifs to incorporate alkyne tags, generating fully functionalized probes for future chemical biology applications. Finally, we establish a workflow for determining the absolute configuration of enantioenriched vinyl sulfoximines and sulfonimidamides by comparing experimentally and computationally determined electronic circular dichroism spectra, enabling access to configurationally assigned enantiomeric pairs by separation.

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Section: Resultsmentioning

confidence: 99%

Synthesis and Configurational Assignment of Vinyl Sulfoximines and Sulfonimidamides

Craven¹,

Briggs²,

Zammit³

et al. 2021

Preprint

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“…While this reaction has been studied with a large variety of early and late transition metal catalysts, achieving selectivity for the formation of the Markovnikov addition product still remains a challenge [35][36][37]. Additionally, most transition metal catalysts have a limited substrate scope, proceeding with low conversions when using aliphatic thiols [38][39][40][41][42][43][44]. Hence, the hydrothiolation of terminal alkynes was studied using the cyclopentadienyl based actinide catalysts 1 and 4 ( Figure 2) [45][46][47].…”

Section: Hydrothiolation Of Terminal Alkynesmentioning

confidence: 99%

Catalytic Organic Transformations Mediated by Actinide Complexes

2015

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This review article presents the development of organoactinides and actinide coordination complexes as catalysts for homogeneous organic transformations. This chapter introduces the basic principles of actinide catalysis and deals with the historic development of actinide complexes in catalytic processes. The application of organoactinides in homogeneous catalysis is exemplified in the hydroelementation reactions, such as the hydroamination, hydrosilylation, hydroalkoxylation and hydrothiolation of alkynes. Additionally, the use of actinide coordination complexes for the catalytic polymerization of α-olefins and the ring opening polymerization of cyclic esters is presented. The last part of this review article highlights novel catalytic transformations mediated by actinide compounds and gives an outlook to the further potential of this field.

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“…Increasing demand for alkenyl sulfides in material science, organic, and bioorganic chemistry has furthered the development of new synthetic methods [6,[18][19][20][21]. The addition of thiols to alkynes is considered as one of the straightforward methods to obtain vinyl sulphides either catalyzed by transition metal complexes [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39], or base-promoted [40][41][42][43][44] and/or through free radicals [21,[45][46][47][48]. This reaction is often judged as a part of "click chemistry" and a process of high atom economy [49,50].…”

Section: Introductionmentioning

confidence: 99%

In Quest of “Stereoselective Switch” for On-Water Hydrothiolation of Terminal Alkynes Using Different Additives and Green Synthesis of Vicinal Dithioethers

Basu

Biswas

Kundu

et al. 2014

Organic Chemistry International

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On-water hydrothiolation reaction between terminal alkyne and thiol has been probed in the presence of various additives. Aromatic alkynes yield corresponding 1-alkenyl sulfides, whereas aliphatic alkynes undergo double-addition yielding vicinal disulfides in good to excellent yields. Formation of 1-alkenyl sulfides proceeds with a high degree of regioselectivity (via anti-Markovnikov addition), and switching the stereoselectivity between E/Z isomers has been noticeably realized in the presence of different additives/promoters.

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Rhodium‐Catalyzed Alkyne Hydrothiolation with Aromatic and Aliphatic Thiols.

Cited by 3 publications

References 2 publications

Synthesis and Configurational Assignment of Vinyl Sulfoximines and Sulfonimidamides

Synthesis and Configurational Assignment of Vinyl Sulfoximines and Sulfonimidamides

Catalytic Organic Transformations Mediated by Actinide Complexes

In Quest of “Stereoselective Switch” for On-Water Hydrothiolation of Terminal Alkynes Using Different Additives and Green Synthesis of Vicinal Dithioethers

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