A highly stereoselective synthesis of glycidic amides based on a new class of chiral sulfonium salts: applications in asymmetric synthesis.

@article{Sarabia2012AHS,
  title={A highly stereoselective synthesis of glycidic amides based on a new class of chiral sulfonium salts: applications in asymmetric synthesis.},
  author={Francisco Sarabia and Carlos Vivar-Garc{\'i}a and Miguel A. Garc{\'i}a-Castro and Cristina Garc{\'i}a-Ruiz and Francisca Mart{\'i}n-G{\'a}lvez and Antonio S{\'a}nchez-Ruiz and Samy Chammaa},
  journal={Chemistry},
  year={2012},
  volume={18 47},
  pages={
          15190-201
        }
}
A new type of chiral sulfonium salts that are characterized by a bicyclic system has been designed and synthesized from α-amino acids. Their corresponding ylides, which were prepared by basic treatment of the sulfonium salts, reacted smoothly with a broad array of simple and chiral aldehydes to provide trans-epoxy amides in reasonable to very good yields and excellent stereoselectivities (>98%). The obtained epoxy amides were found to be useful as synthetic building blocks. Thus, they were… 
Exploring the Reactivity of Chiral Glycidic Amides for Their Applications in Synthesis of Bioactive Compounds
A new class of chiral sulfonium salts, derived from L- and D-methionine, has been designed and successfully employed in our laboratories for the diastereoselective synthesis of glycidic amides. The
Oxazolidine Sulfur Ylides Derived from Phenylglycinol for the Specific and Highly Diastereoselective Synthesis of Aryl and Alkyl trans‐Epoxyamides
Aryl and alkyl chiral oxazolidine sulfonium salts with cis and trans dispositions derived from (–)-(R)-2-phenylglycinol were demonstrated to be good to excellent chiral auxiliaries for the
Stereoselective Synthesis of Trisubstituted Epoxides Marks the Route to Chiral Building Blocks with Quaternary Centers
A facile access to enantiomerically pure derivatives of α-hydroxy-β-amino acids bearing a quaternary center and trifluoromethylated tertiary alcohols which represent highly important building blocks
Stereoselective Total Synthesis of (-)-Depudecin.
TLDR
The total synthesis of the natural product depudecin, an antiangiogenic microbial polyketide with inhibitory activity against histone deacetylases, is reported, efficiently accomplished by a novel asymmetric methodology of epoxide formation based on a new class of chiral sulfonium salts.
Catalytic Asymmetric Synthesis of Chiral Dihydrobenzofurans through a Formal [4+1] Annulation Reaction of Sulfur Ylides and In Situ Generated ortho‐Quinone Methides
The first example of a catalytic asymmetric formal [4+1] annulation reaction between sulfur ylides and in situ generated ortho-quinone methides (o-QMs) is reported in this work. A C2-symmetric chiral
Catalytic Asymmetric Ring-Opening/Cyclopropanation of Cyclic Sulfur Ylides: Construction of Sulfur-Containing Spirocyclopropyloxindoles with Three Vicinal Stereocenters.
A highly efficient asymmetric ring-opening/cyclopropanation reaction of ( E)-3-(oxyethylidene)-2-oxoindolines with 1-alkyl-3-oxotetrahydro-1 H-thiophen-1-ium salts as cyclic sulfur ylides was
Epi-, epoxy-, and C2-modified bengamides: synthesis and biological evaluation.
TLDR
Biological evaluation of all of these bengamide E analogues demonstrated that the polyketide chain is essential for the antitumor activity of these natural products, not being amenable to structural or configurational modifications.
An Olefin Cross-Metathesis Approach to Depudecin and Stereoisomeric Analogues.
A new total synthesis of the natural product (-)-depudecin, a unique and unexplored histone deacetylase (HDAC) inhibitor, is reported. A key feature of the synthesis is the utilization of an olefin
...
...

References

SHOWING 1-10 OF 102 REFERENCES
Cyclic sulfur ylides derived from Gleason-type chiral auxiliaries for the asymmetric synthesis of epoxy amides.
TLDR
Gleason-type chiral auxiliaries were used for the synthesis of a novel class of sulfonium salts, obtained via methylation of the sulfide with Meerwein's salt, which were reduced to their corresponding epoxy alcohols in excellent enantiomeric excesses.
Chiral sulfur ylides for the synthesis of bengamide E and analogues.
TLDR
A new synthetic methodology of asymmetric epoxidation developed in the laboratories has been employed for the stereoselective synthesis of bengamide E and analogues at the terminal olefinic position and allowed access to the generation of a wide array of new bENGamide analogues.
A novel chiral sulfonium yilde: highly enantioselective synthesis of vinylcyclopropanes.
TLDR
A newly designed chiral sulfonium allylide reacted with alpha,beta-unsaturated esters, ketones, amides, and nitriles to afford trans-2-silylvinyl-trans-3-substituted cyclopropyl esters and excellent enantioselectivity in good to high yields.
Highly enantioselective synthesis of glycidic amides using camphor-derived sulfonium salts. Mechanism and applications in synthesis.
TLDR
A combination of crossover experiments and theoretical calculations has revealed that the rate- and selectivity-determining step is ring closure, not betaine formation as was the case for phenyl-stabilized ylides.
Sulfur-ylide-mediated synthesis of functionalized and trisubstituted epoxides with high enantioselectivity; application to the synthesis of CDP-840.
TLDR
A practical, catalytic, and asymmetric conversion of aldehydes into epoxides by using the sulfide 1 (Scheme 1) is reported, obtained in four steps in 48% overall yield from camphorsulfonyl chloride.
New chiral synthons for efficient introduction of bispropionates via stereospecific oxonia-cope rearrangements.
TLDR
The efficacy of this methodology is demonstrated in a short synthesis of invictolide beginning with 2 and (R)-2-methylpentanal, under mild conditions and with complete stereospecificity.
Epoxyamide-based strategy for the synthesis of polypropionate-type frameworks.
TLDR
Several aldehydes showed remarkable stereofacial differentiation, providing a major diastereoisomer, in contrast to others that displayed a poor or no stereoselectivity, enhancing the synthetic value of this new methodology for the preparation of typical polypropionate frameworks found in many natural products.
Highly enantioselective darzens reaction of a camphor-derived sulfonium amide to give glycidic amides and their applications in synthesis.
TLDR
It is discovered that the camphor-derived amide-stabilized sulfonium ylide reacts with aldehydes at -50 degrees C in ethanol to give glycidic amides in one step with up to 99% ee and complete diastereoselectivity.
...
...