N-Alkoxybenzenesulfinamides.  Evidence for an alkylation reaction

Maricich, Tom J.; Jourdenais, Richard A.; Albright, Thomas A.

doi:10.1021/ja00798a101

Cited by 26 publications

(11 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Importantly for medicinal chemists, a range of heteroaryl organometallic reagents performed well, allowing the synthesis of 2- and 3-pyridyl and pyrimidyl sulfonimidamides ( 3ab – ae ). Five-membered heterocycles such as thiophene and benzofuran were incorporated in high yields ( 3af , ag ), as was highly base-sensitive 4-isoxazole 31 ( 3ah ), demonstrating the mildness of the reaction conditions. As with the sulfoximines, alkyl Grignard reagents gave good yields of products ( 3ai – am ).…”

Section: Resultsmentioning

confidence: 99%

Harnessing Sulfinyl Nitrenes: A Unified One-Pot Synthesis of Sulfoximines and Sulfonimidamides

et al. 2020

View full text Add to dashboard Cite

Sulfoximines and sulfonimidamides are promising compounds for medicinal and agrochemistry. As monoaza analogues of sulfones and sulfonamides, respectively, they combine good physicochemical properties, high stability, and the ability to build complexity from a three-dimensional core. However, a lack of quick and efficient methods to prepare these compounds has hindered their uptake in molecule discovery programmes. Herein, we describe a unified, one-pot approach to both sulfoximines and sulfonimidamides, which exploits the high electrophilicity of sulfinyl nitrenes. We generate these rare reactive intermediates from a novel sulfinylhydroxylamine (R–O–N=S=O) reagent through an N–O bond fragmentation process. Combining sulfinyl nitrenes with carbon and nitrogen nucleophiles enables the synthesis of sulfoximines and sulfonimidamides in a reaction time of just 15 min. Alkyl, (hetero)aryl, and alkenyl organometallic reagents can all be used as the first or second component in the reaction, while primary and secondary amines, and anilines, all react with high efficiency as the second nucleophile. The tolerance of the reaction to steric and electronic factors has allowed for the synthesis of the most diverse set of sulfoximines and sulfonimidamides yet described. Experimental and computational investigations support the intermediacy of sulfinyl nitrenes, with nitrene formation proceeding via a transient triplet intermediate before reaching a planar singlet species.

show abstract

Section: Resultsmentioning

confidence: 99%

Harnessing Sulfinyl Nitrenes: A Unified One-Pot Synthesis of Sulfoximines and Sulfonimidamides

et al. 2020

View full text Add to dashboard Cite

show abstract

“…Maricich and co-workers evidenced in 1973 that, in some cases, sulfinylhydroxylamines underwent spontaneous rearrangement to sulfonimidates, with migration of the alkoxy group from the nitrogen to the sulfur atom. [36] In any case, this alternative route would be of great interest, since sulfonimidates are very interesting chiral and nitrogen-containing compounds. They have also applications in material sciences, as monomers of ™inorganic polymers∫, [37,38] and biochemistry, where they may act as inhibitors of human carbonic anhydrase II.…”

Section: Resultsmentioning

confidence: 99%

“…The proposed mechanism of the rearrangement of sulfinyl hydroxylamines by Maricich and co-workers involves a dissociative step to give a nitrenium cation. [36] One could thus have anticipated a loss of stereochemical information during the rearrangement (Scheme 5).…”

Section: Resultsmentioning

confidence: 99%

Iodine(III)‐Mediated Preparations of Nitrogen‐Containing Sulfur Derivatives: Dramatic Influence of the Sulfur Oxidation State

Leca

Song

Amatore

et al. 2004

Chemistry A European J

View full text Add to dashboard Cite

Reaction of sulfonamides with iodosobenzene leads to phenyliodinanes. A new catalysis reaction of the decomposition of these products in the presence of sulfoxides that allows the smooth synthesis of sulfoximines has been evidenced and studied: copper(II) salts were used to prepare compounds 4 a-j and 5 b, d, f, j, k from the corresponding, easily prepared, sulfoxides. The reactions proceed with retention of configuration at the sulfur center, and copper(II) triflate is the best candidate for the catalyst for the imination. Switching from sulfonamides to sulfinamides in the preparation of the starting iodinanes completely alters the reaction pathway: iodinanes are no longer accessible, and sulfonimidates 7 a-j are obtained instead. This behavior can be rationalized by the increase in pK(a) brought about by the removal of one oxygen atom from the sulfur center. Sulfonimidates are interesting molecules with varied applications. Optimization of their one-pot synthesis has been achieved by carrying out the reaction in acetonitrile. The stereochemical study has shown that the transformation proceeds with global retention of the configuration at the sulfur center, albeit with erosion of the enantiomeric purity. A model accounting for this outcome is proposed. In addition, the presence of oxidized sulfonamide by-products has been explained, and this latter pathway becomes the sole one when alcohol is replaced by water. Good yields of the oxidized products are obtained.

show abstract

“…9 Our attention was attracted by an isolated 1973 report by Maricich, who evidenced that, in some cases, sulfinylhy- droxylamines 3 underwent spontaneous rearrangement to the sulfonimidates 2, in which the OR 2 group migrated from nitrogen to sulfur (Scheme 2). 10 Compounds 3 are moderately stable and can be stored for only a few days. They were obtained by coupling sulfinyl chlorides and hydroxylamines, i.e.…”

mentioning

confidence: 99%