Use of Lithiated Chiral <i>o</i>‑Sulfinylbenzyl Carbanions for the One-Pot Building of Linear Fragments Containing up to Four Connected Stereocenters

The reaction of <i>o</i>-sulfinylbenzyl carbanions with prochiral Michael acceptors, such as differently sized cycloalkenones, proceeded with high levels of stereoselectivity, generating molecules containing up to three asymmetric carbon centers in just one synthetic step. All these reactions involved the use of either a proton or an acylating reagent as the final electrophile. Furthermore, the trapping of the enolate resulting from Michael addition with prochiral electrophiles, such as aldehydes or <i>N</i>-sulfonylimines, allowed the highly stereoselective synthesis of densely functionalized compounds containing four chiral centers in just a one-pot sequence, the stereochemical outcome of the sequence being controlled by the sulfinyl auxiliary

Use of Lithiated Chiral <i>o</i>‑Sulfinylbenzyl Carbanions for the One-Pot Building of Linear Fragments Containing up to Four Connected Stereocenters

The reaction of <i>o</i>-sulfinylbenzyl carbanions with prochiral Michael acceptors, such as differently sized cycloalkenones, proceeded with high levels of stereoselectivity, generating molecules containing up to three asymmetric carbon centers in just one synthetic step. All these reactions involved the use of either a proton or an acylating reagent as the final electrophile. Furthermore, the trapping of the enolate resulting from Michael addition with prochiral electrophiles, such as aldehydes or <i>N</i>-sulfonylimines, allowed the highly stereoselective synthesis of densely functionalized compounds containing four chiral centers in just a one-pot sequence, the stereochemical outcome of the sequence being controlled by the sulfinyl auxiliary

Use of Lithiated Chiral <i>o</i>‑Sulfinylbenzyl Carbanions for the One-Pot Building of Linear Fragments Containing up to Four Connected Stereocenters

The reaction of <i>o</i>-sulfinylbenzyl carbanions with prochiral Michael acceptors, such as differently sized cycloalkenones, proceeded with high levels of stereoselectivity, generating molecules containing up to three asymmetric carbon centers in just one synthetic step. All these reactions involved the use of either a proton or an acylating reagent as the final electrophile. Furthermore, the trapping of the enolate resulting from Michael addition with prochiral electrophiles, such as aldehydes or <i>N</i>-sulfonylimines, allowed the highly stereoselective synthesis of densely functionalized compounds containing four chiral centers in just a one-pot sequence, the stereochemical outcome of the sequence being controlled by the sulfinyl auxiliary

Use of Lithiated Chiral <i>o</i>‑Sulfinylbenzyl Carbanions for the One-Pot Building of Linear Fragments Containing up to Four Connected Stereocenters

The reaction of <i>o</i>-sulfinylbenzyl carbanions with prochiral Michael acceptors, such as differently sized cycloalkenones, proceeded with high levels of stereoselectivity, generating molecules containing up to three asymmetric carbon centers in just one synthetic step. All these reactions involved the use of either a proton or an acylating reagent as the final electrophile. Furthermore, the trapping of the enolate resulting from Michael addition with prochiral electrophiles, such as aldehydes or <i>N</i>-sulfonylimines, allowed the highly stereoselective synthesis of densely functionalized compounds containing four chiral centers in just a one-pot sequence, the stereochemical outcome of the sequence being controlled by the sulfinyl auxiliary

Use of Lithiated Chiral <i>o</i>‑Sulfinylbenzyl Carbanions for the One-Pot Building of Linear Fragments Containing up to Four Connected Stereocenters

The reaction of <i>o</i>-sulfinylbenzyl carbanions with prochiral Michael acceptors, such as differently sized cycloalkenones, proceeded with high levels of stereoselectivity, generating molecules containing up to three asymmetric carbon centers in just one synthetic step. All these reactions involved the use of either a proton or an acylating reagent as the final electrophile. Furthermore, the trapping of the enolate resulting from Michael addition with prochiral electrophiles, such as aldehydes or <i>N</i>-sulfonylimines, allowed the highly stereoselective synthesis of densely functionalized compounds containing four chiral centers in just a one-pot sequence, the stereochemical outcome of the sequence being controlled by the sulfinyl auxiliary

Asymmetric Intramolecular Pauson–Khand Reaction Mediated by a Remote Sulfenyl or Sulfinyl Group

In this work, we report the use of the asymmetric intramolecular Pauson–Khand reactions of 4-aryl-4-cyano-1,6-enynes for obtaining enantiomerically enriched bicyclo[3.3.0]­octenones, and the influence of both the quaternary stereocenter and the sulfur functions located at <i>ortho</i>-position of the aryl group, on their stereoselectivity and reactivity. The sulfenyl derivatives bearing substituted or unsubstituted triple bonds and mono- and disubstituted alkene moieties afford bicyclo[3.3.0]­octenones in high yields with complete diastereocontrol. These results are explained by assuming the association of the lone electron pair at sulfur to the Co–alkyne complexes

Synthesis of Enantiomerically Pure <i>anti</i>-1,2-Diaryl and <i>syn</i>-1,2-Alkylaryl <i>vic</i>-Selenoamines

Phenylselenyl benzylcarbanion stabilized by an (<i>S</i>)-2-<i>p</i>-tolylsulfinyl group evolves in a highly stereoselective way in the reactions with (<i>S</i>)-<i>N</i>-(<i>p</i>-tolylsulfinyl)­imines at −98 °C affording diastereomerically pure 1,2-selenoamino derivatives in good yields. The <i>syn</i> or <i>anti</i> relationship of the obtained compounds depends on the alkyl or aryl character of the imine. They are easily transformed into enantiomerically pure (1<i>R</i>,2<i>S</i>)-1-aryl­[or (1<i>S</i>,2<i>S</i>)-1-alkyl]-2-(phenylseleno)-2-phenylethylamines by reaction with <i>t-</i>BuLi and subsequent methanolysis of the generated sulfinamide derivatives with TFA