Synthesis of Optically Pure 1,2-Diaryl- and 1,2-Alkylaryl-1,2-amino Sulfides

Arroyo, Yolanda; Meana, Angela; Rodriguez, J.F.; Santos, Mercedes; Sanz‐Tejedor, M. Ascension; Ruano, José Luis Garcı́a

doi:10.1021/jo050129x

Cited by 37 publications

(25 citation statements)

References 34 publications

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“…Compounds 1 and 2 had been previously synthesised. [5][6][7][8] The procedure used to synthesise imines 3 is reported in the Supporting Information. The NMR spectra of some representative compounds of Tables 2-6 and Scheme 4 can be found in the Supporting Information as well as the ORTEP structures of compounds 5 i, syn-7 i and anti-6' b.…”

Section: Methodsmentioning

confidence: 99%

“…Both compounds exhibit the same configuration at the benzylic carbon atom next to the sulfinyl group (C2), which completely controls the stereoselectivity at this position, as has been observed in the reactions of (S)-2 with all the electrophiles studied so far. [5][6][7][8]12] Compounds anti-6 and syn-7 differ in the configuration of the aminic carbon atom Table 2. Table 3.…”

Section: The Plot Of Log a C H T U N G T R E N N U N G {[(Ss S )-4]/mentioning

confidence: 99%

“…This would complement well the previously reported method of preparing epimers with an S configuration at C1 (anti derivatives starting from (S)-2 using (S)-N-sulfinylimines as electrophiles). [5][6][7][8] It would be desirable for the aryl group joined to the nitrogen atom to be easily removed, thus allowing the synthesis of free amines. We believe that 2,4,6-trimethoxyaniline would be a good candidate because the N-aryl ring could be easily eliminated by an oxidative method.…”

Section: Stereochemical Modelmentioning

confidence: 99%

“…These reactions were also successfully used in the synthesis of 1,2-aminalcohols [6,7] and sulfides, [8] starting from the corresponding oxygenated and sulfurated carbanions.…”

Section: Introductionmentioning

confidence: 99%

“…[5][6][7][8] However, the method was not appropriate for obtaining syn derivatives because the reactions of reagents with opposite configurations at their sulfinyl groups (mismatched pair) yielded mixtures of isomers (lefthand equation, Scheme 1). These results have been explained by a stereochemical model based exclusively on steric effects [5][6][7][8] (see below). With the aim of searching for an alternative method to the synthesis of syn diastereoisomers we decided to investigate the reactions of the carbanions derived from (S)-1 and (S)-2 (Scheme 2) with other imine derivatives by using a single asymmetric induction procedure.…”

Section: Introductionmentioning

confidence: 99%

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π–π Stacking versus Steric Effects in Stereoselectivity Control: Highly Diastereoselective Synthesis of syn‐1,2‐Diarylpropylamines

Ruano

Alemán

Alonso

et al. 2007

Chemistry A European J

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N-Arylarylideneamines react with sulfinylbenzyl carbanions derived from 2-(p-tolylsulfinyl)toluenes (S)-1 and (S)-2, affording epimeric mixtures at C1 of 1,2-diarylethyl- and 1,2-diarylpropylamine derivatives. The sulfinyl group completely controls the configuration at C2 in the reactions of (S)-2. The configuration at C1 depends on the electron density of the ring adjacent to the iminic carbon atom which is modulated by pi-pi stacking interactions with the ring joined to the carbanionic centre. The stereoselectivity was controlled by modifying the acceptor character of the arylideneamine ring with appropriate substituents, the formation of the highly selective (R) configuration at C1 being made possible by electron-donating groups. N-(2,4,6-Trimethoxyphenyl)arylideneamines have been shown to be suitable starting materials for the preparation of (R)-1,2-diarylethyl- and (1R,2S)-1,2-diarylpropylamines (syn epimers) in a highly stereoselective manner.

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Section: Methodsmentioning

confidence: 99%

Section: The Plot Of Log a C H T U N G T R E N N U N G {[(Ss S )-4]/mentioning

confidence: 99%

Section: Stereochemical Modelmentioning

confidence: 99%

“…These reactions were also successfully used in the synthesis of 1,2-aminalcohols [6,7] and sulfides, [8] starting from the corresponding oxygenated and sulfurated carbanions.…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

π–π Stacking versus Steric Effects in Stereoselectivity Control: Highly Diastereoselective Synthesis of syn‐1,2‐Diarylpropylamines

Ruano

Alemán

Alonso

et al. 2007

Chemistry A European J

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Addition of Non‐Stabilized Carbon‐Based Nucleophilic Reagents to Chiral N ‐Sulfinyl Imines

et al. 2019

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Natural products and pharmaceuticals that contain chiral branched amines are compounds of considerable interest. One strategy for preparing chiral branched amines involves the addition of a nucleophile to an imine bearing a readily cleavable chiral auxiliary. Sulfinamide‐based auxiliaries are well‐suited to this approach because (i) many sulfonamides are commercially available or can be prepared by efficient synthetic methods, (ii) N ‐sulfinyl aldimines and ketimines can be prepared in a straightforward manner, (iii) the chiral amine products are obtained with high diastereomeric ratios across a wide range of carbon‐based nucleophiles, and (iv) the N ‐sulfinyl group is cleaved under mild conditions. This chapter focuses on the addition of non‐stabilized, carbon‐based nucleophiles to N ‐sulfinyl aldimines and ketimines. Specifically, additions of alkyl, alkenyl, aryl, allylic, propargylic, alkynyl, and cyano nucleophiles are presented. Factors that can influence the stereoselectivity of the addition reaction are presented, along with the most prevalent reaction conditions employed for each class of nucleophile. Nucleophilic additions to N ‐sulfinyl aldimines and ketimines are key steps in the syntheses of a number of drug discovery targets and natural products, examples of which are highlighted in this review.

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