Pseudopeptidic sulfoxides: relative stability and absolute configuration of diastereomers

Poudrel, Jean-Marc; Karuso, Peter

doi:10.1016/s0040-4039(00)01003-0

Cited by 3 publications

(2 citation statements)

References 11 publications

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“…A sulfenic acid generation explains the decomposition in CHCl 3 solution of the S-epimers of pseudopeptidic sulfoxides synthesized by Karuso et al [55], to be utilized as FKBP (FK506-binding proteine) inhibitors. It is suggested that the S-configuration could be directly related to the different stability of the epimeric sulfoxides.…”

Section: Extrusion Of Sulfenic Acidsmentioning

confidence: 99%

Recent Advances and Perspectives in the Chemistry of Sulfenic Acids

Aversa¹,

Barattucci²,

Bonaccorsi³

et al. 2007

COC

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This review provides a comprehensive survey of the literature on sulfenic acid chemistry from 1990 through June 2006, focusing the attention on salient aspects of their structures and involvement in organic processes. Even if the majority of known sulfenic acids cannot be isolated, some stable ones have been obtained, and their study helped dramatically the comprehension of chemical and physical properties of all sulfenic acids and indirectly of the role that Cys-SOHs play in protein biochemistry. Many papers have been published in the last fifteen years about the sulfenic acid intermediacy in organic chemistry. Once generated, they can be involved in intra-and intermolecular additions to unsaturated molecules. Few examples of sulfenic acid addition to double bonds have been recently described and most of them are intramolecular processes, whereas the addition of enantiopure sulfenic acids onto carbon-carbon triple bonds has been widely exploited in the synthesis of vinyl sulfoxides to be used in many stereoselective transformations. The thermicelimination from sulfinyl precursors is a way to generate sulfenic acids but it has been also used for removing the sulfinyl moiety from organic molecules and forming double bonds with controlled stereochemistry. Some significant applications of extrusion processes are also described in the present review.

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Section: Extrusion Of Sulfenic Acidsmentioning

confidence: 99%

Recent Advances and Perspectives in the Chemistry of Sulfenic Acids

Aversa¹,

Barattucci²,

Bonaccorsi³

et al. 2007

COC

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“…The oxidation of homochiral β-amino sulfides has been employed the most extensively, presumably since the protocol gives the most rapid access to sulfoxide by way of a readily accessible amino sulfide ( D ). ,,− ,,− ,− Surprisingly, despite the presence of the stereogenic carbon, the diastereoselection of oxidation protocols has only rarely exceeded dr values of 90%. ,, In most cases, ratios range from 1:1 to 3:2, ,,,,,,− , and on many occasions, diastereoselectivities are not even reported or acknowledged. ,,,,− In the few instances when an asymmetric oxidizing agent was employed to complement the stereogenic carbon in the substrate, selected de values reach 95% but only for particular substrates and conditions. ,− …”

Section: Introductionmentioning

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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Elimination, ring-contraction, and fragmentation reactions of 1-thioflavanone 1-oxides

Somogyi¹

2001

Can. J. Chem.

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Epimeric thioflavanone sulfoxides (2b) were selectively transformed into thioflavone (1a), thioaurone (3a), and di(2-cinnamoylphenyl) disulfide (4). Disulfide 4 can be recyclized into thioaurones (3ac) and thioflavanones (2a,5) with heterolysis of the SS bond. The 3-p-anisylidene sulfoxide analog of 2b (6) transforms, with fragmentation, into 4'-methoxythioaurone 3b.Key words: chalcone, ring contraction, sulfoxides, thioaurones, thioflavonoids.

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Pseudopeptidic sulfoxides: relative stability and absolute configuration of diastereomers

Cited by 3 publications

References 11 publications

Recent Advances and Perspectives in the Chemistry of Sulfenic Acids

Recent Advances and Perspectives in the Chemistry of Sulfenic Acids

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

Elimination, ring-contraction, and fragmentation reactions of 1-thioflavanone 1-oxides

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