Discoveries in Sulfenic Acid Anion Chemistry

Schwan, Adrian L.; Söderman, Stefan C.

doi:10.1080/10426507.2012.729116

Cited by 23 publications

(5 citation statements)

References 35 publications

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“…Ethyl 2-naphtyl sulfoxide (5a) proved to be a suitable coupling partner, despite affording 3a in lower yield (Table 2, 5a). As expected, the other three alkyl sulfoxides under investigation (5bd) only generated trace amounts of 3a, presumably owing to rapid formation of sulfenate anions after attack of methoxide on the sulfur [46][47][48] (Table 2, 5b-5d).…”

Section: Resultssupporting

confidence: 70%

Transition-metal-free formal cross-coupling of aryl methyl sulfoxides and alcohols via nucleophilic activation of C-S bond

Nieves‐Quinones

Zhang

et al. 2020

Nat Commun

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Employment of sulfoxides as electrophiles in cross-coupling reactions remains underexplored. Herein we report a transition-metal-free cross-coupling strategy utilizing aryl (heteroaryl) methyl sulfoxides and alcohols to afford alkyl aryl(heteroaryl) ethers. Two drug molecules were successfully prepared using this protocol as a key step, emphasizing its potential utility in medicinal chemistry. A DFT computational study suggests that the reaction proceeds via initial addition of the alkoxide to the sulfoxide. This adduct facilitates further intramolecular addition of the alkoxide to the aromatic ring wherein charge on the aromatic system is stabilized by the nearby potassium cation. Rate-determining fragmentation then delivers methyl sulfenate and the aryl or heteroaryl ether. This study establishes the feasibility of nucleophilic addition to an appended sulfoxide as a means to form a bond to aryl (heteroaryl) systems and this modality is expected to find use with many other electrophiles and nucleophiles leading to new cross-coupling processes.

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Section: Resultssupporting

confidence: 70%

Transition-metal-free formal cross-coupling of aryl methyl sulfoxides and alcohols via nucleophilic activation of C-S bond

Nieves‐Quinones

Zhang

et al. 2020

Nat Commun

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“…With more and more new bioactive organosulfur compounds being discovered and used in the clinic, organosulfur chemistry, especially chiral organosulfur chemistry, is developing rapidly. , Sulfinate anions (RSO – ), − a class of new reactive organosulfur intermediates, have recently displayed valuable applications in enantioselective reactions and cross-coupling reactions.…”

mentioning

confidence: 99%

Unusual Deoxidative Coupling Reaction of β-Sulfinyl Esters with Benzylic Trimethylammonium Salts

et al. 2021

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A KOH-promoted unusual deoxidative coupling reaction of β-sulfinyl esters with benzylic trimethylammonium salts to produce thioethers is discovered for the first time. If quaternary ammonium salts synthesized from enantiomerically enriched amines are adopted, highly enantiomerically enriched benzyl thioethers (>95–99% ee) with configurations opposite to those of the enantiomerically enriched amines are obtained.

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“…The protocol requires the addition of a nucleophile to a β-sulfinyl acrylate, and several options are available . A number of reactions were performed, with variation of the nucleophile and other parameters, and the outcome of these key experiments has been summarized previously. , …”

Section: Resultsmentioning

confidence: 99%

Sulfenate Substitution as a Complement and Alternative to Sulfoxidation in the Diastereoselective Preparation of Chiral β-Substituted β-Amino Sulfoxides

Söderman

Schwan

2013

J. Org. Chem.

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Building from a previous communication, the reaction of sulfenate anions with chiral N-Boc-protected β-substituted β-amino iodides was evaluated as a conceptually different synthetic approach to chiral β-substituted β-amino sulfoxides. Using arenesulfenates, yields typically ranged from 71% to 92%, and dr's were often near 9:1. Alkanesulfenates proved less reactive, delivering lower yields and dr's. 1-Alkenesulfenates demonstrated high reactivity, returning chemical yields of 60-86% and dr's often close to 9:1 and as high as 95:5. (S)-β-Amino iodide electrophiles yielded (R(S),S(C))-β-amino sulfoxides, whereas (R)-amino iodides afford (S(S),R(C))-β-amino sulfoxides. The absolute configuration of the products makes the sulfenate protocol complementary to other existing preparations, including the commonly employed sulfoxidation of β-amino sulfides. The reactivity of N-Boc-protected 2-benzyl-2-aminoethyl iodide was found to be superior to the less sterically encumbered n-butyl iodide. A transition state model is proposed to account for the stereochemistry of the products and also for the high reactivity of the electrophile. Overall, the chemistry represents a new means of introducing sulfur stereogenicity in a molecule.

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Discoveries in Sulfenic Acid Anion Chemistry

Cited by 23 publications

References 35 publications

Transition-metal-free formal cross-coupling of aryl methyl sulfoxides and alcohols via nucleophilic activation of C-S bond

Transition-metal-free formal cross-coupling of aryl methyl sulfoxides and alcohols via nucleophilic activation of C-S bond

Unusual Deoxidative Coupling Reaction of β-Sulfinyl Esters with Benzylic Trimethylammonium Salts

Sulfenate Substitution as a Complement and Alternative to Sulfoxidation in the Diastereoselective Preparation of Chiral β-Substituted β-Amino Sulfoxides

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