Practical and highly stereoselective technology for preparation of enantiopure sulfoxides and sulfinamides utilizing activated and functionally differentiated N-sulfonyl-1,2,3-oxathiazolidine-2-oxide derivatives

Han, Zhengxu S.; Krishnamurthy, Dhileepkumar; Grover, Paul; Fang, Q. Kevin; Su, Xiping; Wilkinson, H. Scott; Lu, Zexi; Magiera, Daniel; Senanayake, Chris H.

doi:10.1016/j.tet.2005.03.122

Cited by 65 publications

(32 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The chiral sulfinyl transfer auxiliary approach developed by Senanayake and coworkers is an alternative general and efficient method for the preparation of a broad range of enantiomerically pure sulfinamides (Scheme 1). 19 Addition of a Grignard reagent to the sulfinyl transfer reagent 1 proceeds with inversion of stereochemistry to give sulfinate ester 2 . Treatment of 2 with an amide nucleophile then provides sulfinamide 3 and the chiral auxiliary 4 , which then can be recycled back to the sulfinyl transfer reagent 1 by reaction with thionyl chloride.…”

Section: Resultsmentioning

confidence: 99%

“…However, control experiments also established that 8 was not stable to concentrated NH 4 OH even at rt. LiHMDS is one of the most commonly used nucleophiles for sulfinate ester cleavage 19 and was next investigated. Addition of 5 equiv of LHMDS provided sulfinamide 8 in 59% yield after chromatography (entry 3).…”

Section: Resultsmentioning

confidence: 99%

“…19 Condensation with ethyl glyoxylate to provide the corresponding N -perfluorobutanesulfinyl imino ester is also described. We further report that the enhanced electrophilicity of this N -perfluorobutanesulfinyl imino ester enables transformations to be performed that are shown not to proceed with the corresponding N - tert -butanesulfinyl imino ester.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Preparation of Enantiomerically Pure Perfluorobutanesulfinamide and Its Application to the Asymmetric Synthesis of α-Amino Acids

et al. 2016

View full text Add to dashboard Cite

A high yielding and practical two-step synthesis of enantiomerically pure perfluorobutanesulfinamide from Senanayake’s 2-aminoindanol-derived sulfinyl transfer reagent was developed and carried out on multi-gram scale. Straightforward condensation of this sulfinamide with ethyl glyoxylate provided the N-perfluorobutanesulfinyl imino ester. The utility of this activated N-sulfinyl imino ester was demonstrated for reactions that either gave no product or very low yields with the corresponding less electrophilic N-tert-butanesulfinyl derivative. Specifically, the Rh(III)-catalyzed C-H bond addition of aromatic compounds to the N-perfluorobutanesulfinyl imino ester provided arylglycines with very high diastereoselectivities for a range of directing groups including pyrrolidine amide, azo, sulfoximine, 1-pyrazole and 1,2,3-triazole functionality. Thermal asymmetric aza-Diels Alder reactions also proceeded in good yields and with high selectivity, including for the substituted dienes (E)-1,3-pentadiene and (2E, 4E)-2,4-hexadiene.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Preparation of Enantiomerically Pure Perfluorobutanesulfinamide and Its Application to the Asymmetric Synthesis of α-Amino Acids

et al. 2016

View full text Add to dashboard Cite

show abstract

“…In 2005, the Senanayake group described a process in which (+)-norephedrine-derived oxathiazolidine 2-oxides are used as sulfinyl transfer agents in the synthesis of optically pure sulfoxides and sulfinamides [ 48 ]. The application of this method to the synthesis of our chiral sulfoxide tethers is presented in Scheme 4 .…”

Section: Resultsmentioning

confidence: 99%

Chiral cyclopentadienylruthenium sulfoxide catalysts for asymmetric redox bicycloisomerization

Trost¹,

Ryan²,

Rao³

2016

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

SummaryA full account of our efforts toward an asymmetric redox bicycloisomerization reaction is presented in this article. Cyclopentadienylruthenium (CpRu) complexes containing tethered chiral sulfoxides were synthesized via an oxidative [3 + 2] cycloaddition reaction between an alkyne and an allylruthenium complex. Sulfoxide complex 1 containing a p-anisole moiety on its sulfoxide proved to be the most efficient and selective catalyst for the asymmetric redox bicycloisomerization of 1,6- and 1,7-enynes. This complex was used to synthesize a broad array of [3.1.0] and [4.1.0] bicycles. Sulfonamide- and phosphoramidate-containing products could be deprotected under reducing conditions. Catalysis performed with enantiomerically enriched propargyl alcohols revealed a matched/mismatched effect that was strongly dependent on the nature of the solvent.

show abstract

“…Therefore, it is uneconomical and impractical to efficiently produce a large amount of sulfinamides in industry, and this method is not practical. Building upon pioneering work by Wudl and Lee, 24 Snyder and Benson, 25 and Kagan and co-workers, 26 Senanayake and coworkers 27 reported a method of using cis-1-amino-indane-2indanol as a source of chiral auxiliary-based to modularly synthesize enantiomerically pure sulfinamides with different structures (Scheme 8). In addition, this research group has also reported a synthetic method using methamphetamine as a chiral auxiliary (Scheme 9).…”

Section: With Chiral Auxiliariesmentioning

confidence: 99%

Syntheses and Transformations of Sulfinamides

Zhang¹,

Xi²,

He³

et al. 2021

Synthesis

View full text Add to dashboard Cite

Sulfinamides, especially enantiopure sulfinamides, are widely used in organic and medicinal synthesis. Syntheses and transformations of racemic and enantioenriched sulfinamides have achieved great progress. Especially sulfinamides demonstrate interesting and valuable reactivity, which deserves to be concerned. This review summarizes the latest development in the synthesis and transformation of sulfinamides and will be helpful for future related research.

show abstract

Practical and highly stereoselective technology for preparation of enantiopure sulfoxides and sulfinamides utilizing activated and functionally differentiated N-sulfonyl-1,2,3-oxathiazolidine-2-oxide derivatives

Cited by 65 publications

References 47 publications

Preparation of Enantiomerically Pure Perfluorobutanesulfinamide and Its Application to the Asymmetric Synthesis of α-Amino Acids

Preparation of Enantiomerically Pure Perfluorobutanesulfinamide and Its Application to the Asymmetric Synthesis of α-Amino Acids

Chiral cyclopentadienylruthenium sulfoxide catalysts for asymmetric redox bicycloisomerization

Syntheses and Transformations of Sulfinamides

Contact Info

Product

Resources

About