Synthesis of Pseudopeptides with Sulfoximines as Chiral Backbone Modifying Elements

Bolm, Carsten; Moll, Guido; Kahmann, Jan D.

doi:10.1002/1521-3765(20010302)7:5<1118::aid-chem1118>3.0.co;2-3

Cited by 59 publications

(19 citation statements)

References 127 publications

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“…In the syntheses of ( S S , S C )- 18 and ( R S , S C )- 19 we benefited from our expertise in preparing sulfoximine-based pseudopeptides [20–21]. Hence, the reaction of ( S )- 2 with N -Boc protected L-valine, N , N '-dicyclohexylcarbodiimide (DCC) and hydroxybenzotriazole (HOBt) provided (homochiral) ( S S , S C )- 14 in good yield (74%).…”

Section: Resultsmentioning

confidence: 99%

Synthesis of chiral sulfoximine-based thioureas and their application in asymmetric organocatalysis

Frings¹,

Thomé²,

Bolm³

2012

Beilstein J. Org. Chem.

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SummaryFor the first time, chiral sulfoximine derivatives have been applied as asymmetric organocatalysts. In combination with a thiourea-type backbone the sulfonimidoyl moiety leads to organocatalysts showing good reactivity in the catalytic desymmetrization of a cyclic meso-anhydride and moderate enantioselectivity in the catalytic asymmetric Biginelli reaction. Straightforward synthetic routes provide the newly designed thiourea-sulfoximine catalysts in high overall yields without affecting the stereohomogeneity of the sulfur-containing core fragment.

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Section: Resultsmentioning

confidence: 99%

Synthesis of chiral sulfoximine-based thioureas and their application in asymmetric organocatalysis

Frings¹,

Thomé²,

Bolm³

2012

Beilstein J. Org. Chem.

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“…and TsOH (10 mol%) in toluene at 100 °C failed 23. Also the intended simultaneous cleavage of the benzyl and the Cbz groups of 12ba by hydrogenation over Pd/C in methanol24 remained unsuccessful, presumably due to a catalyst deactivation by the substrate 25. In both cases the protected amino acids did not react.…”

Section: Methodsmentioning

confidence: 99%

Methionine and Buthionine Sulfoximines: Syntheses under Mild and Safe Imidation/Oxidation Conditions

2014

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Methionine and buthionine sulfoximines (MSO and BSO) are non-natural amino acids known to inhibit the biosynthesis of glutathione (GSH). The current syntheses of these biologically active molecules involve harsh reaction conditions and the use of hazardous reagents for the sulfur imidation. Here, improved syntheses of MSO and BSO are presented including safe and mild one-pot imidation/oxidation sequences and single-step deprotections of three different functionalities.Methionine sulfoximine (MSO, 1), the first example of a sulfoximine ever described, was isolated from freshly milled wheat that had been treated with nitrogen trichloride. [1] The interesting biological profile of MSO ( Figure 1) attracted immediate attention, [2] and has provided a useful starting point for future/further investigations into the application of sulfoximine derivatives in a medicinal chemistry setting. [3] MSO interacts with g-glutamylcysteine synthetase, which is an essential enzyme in the glutathione (GSH, 3) synthesis, and irreversibly inhibits glutamine synthetase. [4] A Scheme 3. Synthesis of MSO via an N-nosyl sulfoximine.Scheme 4. Synthesis of MSO and BSO via N-acyl sulfoximines.

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“…S ‐Methyl‐ S ‐phenyl sulfoximines ( S )‐ 1 and ( R )‐ 1 were synthesized according to the literature procedure 8. Compounds 2 were prepared by acylation with acyl halides according to the published protocol,9b, 15b and compounds 8 and 9 were synthesized according to general procedure GP1. CH 2 Cl 2 was dried with lithium aluminum hydride and distilled prior to use under an inert atmosphere.…”

Section: Methodsmentioning

confidence: 99%

Synthetic and Spectroscopic Investigation of N‐Acylated Sulfoximines

Hackenberger

Raabe

Bolm

2004

Chemistry A European J

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N-Acylated sulfoximines display unique chemical properties. Various derivatives have been synthesized and investigated by NMR and IR spectroscopy. The results of these studies suggest that the bond between the sulfoximine nitrogen atom and the carbonyl group has a less pronounced double-bond character than the corresponding bond in an amide. This assumption is supported by the first X-ray crystal structure of a sulfoximidoyl derivative. Ab initio calculations (MP2/6-311++G**) provide further insight into the electronic nature of the N-acyl fragment. Studies of the chemical behavior of N-acylated sulfoximines indicate the presence of a highly electrophilic carbonyl group. Thus, the N--C(O) bond can easily be cleaved under mild basic conditions, and the acidity of the hydrogen atoms alpha to the sulfoximine carbonyl group is high. As a consequence of the latter property, endo,endo-sulfoximidoyl norbornene derivatives readily isomerize to their endo,exo counterparts, and sulfoximine-containing pseudopeptides can easily epimerize at the stereogenic center next to the N--C(O) carbonyl group.

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Synthesis of Pseudopeptides with Sulfoximines as Chiral Backbone Modifying Elements

Cited by 59 publications

References 127 publications

Synthesis of chiral sulfoximine-based thioureas and their application in asymmetric organocatalysis

Synthesis of chiral sulfoximine-based thioureas and their application in asymmetric organocatalysis

Methionine and Buthionine Sulfoximines: Syntheses under Mild and Safe Imidation/Oxidation Conditions

Synthetic and Spectroscopic Investigation of N‐Acylated Sulfoximines

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