Nucleophilic substitution at sulfinyl sulfur. Factors affecting the inversion to retention ratio in acid-catalyzed alcoholysis of chiral n,n-di isopropyl -toluenesulfinamide

Mikotajczyk, M.; Drabowicz, I.; Bujnicki, Bogdan

doi:10.1016/s0040-4039(01)80924-2

Cited by 27 publications

(9 citation statements)

References 8 publications

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“…It is remarkable that the N -(diphenylmethylene) group was not removed under these reaction conditions but was trapped by the deprotected β-amino group, as the deprotection of analogous anti -substrates under the same reaction conditions led to unprotected anti -α,β-diaminocarboxyl esters [18]. This is possibly due to the fact that solvolysis of the imine functionality with ethanol is not favorable and an acid-catalyzed deprotection of the sulfinyl moiety will occur first [41–42]. The resulting β-amino deprotected syn -γ-chloro-α,β-diaminocarboxylamide could subsequently ring close further to trans -imidazolidine 12b , which will be less sterically congested than an analogous cis -imidazolidine.…”

Section: Resultsmentioning

confidence: 99%

Asymmetric synthesis of γ-chloro-α,β-diamino- and β,γ-aziridino-α-aminoacylpyrrolidines and -piperidines via stereoselective Mannich-type additions of N-(diphenylmethylene)glycinamides across α-chloro-N-sulfinylimines

Callebaut

Mangelinckx²,

Veken³

et al. 2012

Beilstein J. Org. Chem.

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SummaryThe asymmetric synthesis of new chiral γ-chloro-α,β-diaminocarboxylamide derivatives by highly diastereoselective Mannich-type reactions of N-(diphenylmethylene)glycinamides across chiral α-chloro-N-p-toluenesulfinylaldimines was developed. The resulting (S S,2S,3S)-γ-chloro-α,β-diaminocarboxylamides were formed with the opposite enantiotopic face selectivity as compared to the (S S,2R,3R)-γ-chloro-α,β-diaminocarboxyl esters obtained via Mannich-type addition of analogous N-(diphenylmethylene)glycine esters across a chiral α-chloro-N-p-toluenesulfinylaldimine. Selective deprotection under different acidic reaction conditions and ring closure of the γ-chloro-α,β-diaminocarboxylamides was optimized, which resulted in Nα-deprotected syn-γ-chloro-α,β-diaminocarboxylamides, N-sulfinyl-β,γ-aziridino-α-aminocarboxylamide derivatives, a trans-imidazolidine, and an Nα,Nβ-deprotected syn-γ-chloro-α,β-diaminocarboxylamide.

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Section: Resultsmentioning

confidence: 99%

Asymmetric synthesis of γ-chloro-α,β-diamino- and β,γ-aziridino-α-aminoacylpyrrolidines and -piperidines via stereoselective Mannich-type additions of N-(diphenylmethylene)glycinamides across α-chloro-N-sulfinylimines

Callebaut

Mangelinckx²,

Veken³

et al. 2012

Beilstein J. Org. Chem.

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“…95–101 °C, [α] D = +85.7 (c, 1.82; acetone) [lit. [ 10 ], [α] D = 82.9; mp. 102–103 °C after crystallization from ethyl ether]; 1 H-NMR (60MHz, CDCl 3 ) δ 7.90–7.35 (m, 5H, H -Ar); 3.45 (s, 2H, H 2 N).…”

Section: Methodsmentioning

confidence: 99%

“…In this paper we wish to report the complete results of our detailed investigations of this reaction using a broad spectrum of optically active sulfinamides, alcohols and acidic catalysts and to rationalize the most interesting and unique discovery that its steric course varies from inversion to predominant retention and can be influenced by many factors. Preliminary results of our studies have been reported in two short communications [ 9 , 10 ].…”

Section: Introductionmentioning

confidence: 99%

Acid Catalyzed Alcoholysis of Sulfinamides: Unusual Stereochemistry, Kinetics and a Question of Mechanism Involving Sulfurane Intermediates and Their Pseudorotation

2015

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The synthesis of optically active sulfinic acid esters has been accomplished by the acid catalyzed alcoholysis of optically active sulfinamides. Sulfinates are formed in this reaction with a full or predominant inversion of configuration at chiral sulfur or with predominant retention of configuration. The steric course of the reaction depends mainly on the size of the dialkylamido group in the sulfinamides and of the alcohols used as nucleophilic reagents. It has been found that bulky reaction components preferentially form sulfinates with retention of configuration. It has been demonstrated that the stereochemical outcome of the reaction can be changed from inversion to retention and vice versa by adding inorganic salts to the acidic reaction medium. The unusual stereochemistry of this typical bimolecular nucleophilic substitution reaction, as confirmed by kinetic measurements, has been rationalized in terms of the addition-elimination mechanism, A-E, involving sulfuranes as intermediates which undergo pseudorotations.

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“…The retention of the configuration which is sometimes observed has been attributed to the formation of sulfurane intermediates that undergo rapid pseudorotation (Scheme 3) 23 Moreover, isopropyl alcohol and cyclohexanol, which in the absence of the salt gave predominant retention, in its presence gave mostly inversion.…”

Section: -Naph; 2-naphmentioning

confidence: 99%

Sulfinic acids and their derivatives. Stereochemistry and chiroptical properties

Nudelman

1990

Sulphinic Acids, Esters and Derivatives (1990)

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Nucleophilic substitution at sulfinyl sulfur. Factors affecting the inversion to retention ratio in acid-catalyzed alcoholysis of chiral n,n-di isopropyl -toluenesulfinamide

Cited by 27 publications

References 8 publications

Asymmetric synthesis of γ-chloro-α,β-diamino- and β,γ-aziridino-α-aminoacylpyrrolidines and -piperidines via stereoselective Mannich-type additions of N-(diphenylmethylene)glycinamides across α-chloro-N-sulfinylimines

Asymmetric synthesis of γ-chloro-α,β-diamino- and β,γ-aziridino-α-aminoacylpyrrolidines and -piperidines via stereoselective Mannich-type additions of N-(diphenylmethylene)glycinamides across α-chloro-N-sulfinylimines

Acid Catalyzed Alcoholysis of Sulfinamides: Unusual Stereochemistry, Kinetics and a Question of Mechanism Involving Sulfurane Intermediates and Their Pseudorotation

Sulfinic acids and their derivatives. Stereochemistry and chiroptical properties

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