Asymmetric synthesis of chiral sulfoxides and sulfinimines by using N-sulfinylsultam

Oppolzer, Wolfgang; Froelich, Olivier; Wiaux‐Zamar, Chantal; Bérnardinelli, Gerald

doi:10.1016/s0040-4039(97)00472-3

Cited by 50 publications

(12 citation statements)

References 27 publications

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Section: Introductionmentioning

confidence: 99%

“…Other chiral intermediates have been described for the in situ preparaton of N,N -bis(trimethylsilyl)- p -toluenesulfinamide but are limited by the high costs of the chiral reagents ), but this method is again limited by the unwieldy chromatographic purification to provide diastereomerically pure DAG- tert -butanesulfinate precursor . Davis and co-workers have also demonstrated that stoichiometric oxidations of sulfenimines derived from aromatic aldehydes or acetophenone with chiral oxaziridines can proceed with good enantiocontrol. 7b, However, this method requires stoichiometric amounts of the high molecular weight chiral oxidants.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis of Enantiomerically Pure N-tert-Butanesulfinyl Imines (tert-Butanesulfinimines) by the Direct Condensation of tert-Butanesulfinamide with Aldehydes and Ketones

et al. 1999

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Experimental details for the first general methods for the one-step preparation of N-tert-butanesulfinyl imines (tert-butanesulfinimines) (2) from aldehydes and ketones is described. To effect the condensations of tert-butanesulfinamide (1) with aldehydes, the Lewis acidic dehydrating agents MgSO4, CuSO4, or Ti(OEt)4 are employed. Aldehyde condensations mediated by MgSO4 proceed in high yields (84−96%) when an excess of aldehyde is used. In contrast, only a slight excess of aldehyde (1.1 equiv) relative to tert-butanesulfinamide provides sulfinimines in high yields when the more Lewis acidic dehydrating agent CuSO4 is used. The CuSO4-mediated procedure is effective for a wide range of aldehydes, including sterically demanding aldehydes, such as isobutyraldehyde (90%), and electron-rich aldehydes, such as p-anisaldehyde (81%). The still more Lewis acidic Ti(OEt)4 and Ti(O-i-Pr)4 also afford N-tert-butanesulfinyl aldimines from especially unreactive aldehydes, such as pivaldehyde (82%). In addition, Ti(OEt)4 is effective for the condensation of 1 with ketones to afford a wide range of N-tert-butanesulfinyl ketimines in good yields (77−91%). For sulfinyl ketimines derived from methyl or n-alkyl phenyl ketones and methyl or n-alkyl isopropyl ketones, only the E isomer is detected by 1H and 13C NMR in CDCl3. For those cases where the difference in steric demand about the imine is very small, such as for 2-hexanone, high E/Z ratios are still observed (5:1).

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis of Enantiomerically Pure N-tert-Butanesulfinyl Imines (tert-Butanesulfinimines) by the Direct Condensation of tert-Butanesulfinamide with Aldehydes and Ketones

et al. 1999

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“…249 218 was formed through the 4-dimethylaminopyridine (DMAP) assisted sulfinylation of sultam. Treating 218 with an organometallic reagent in THF at low temperatures resulted in the formation of the sulfoxides, which were obtained in good yield and excellent enantiopurity (Scheme 107).…”

Section: Scheme 106mentioning

confidence: 99%

Synthesis of enantioenriched sulfoxides

O’Mahony¹,

Kelly²,

Lawrence³

et al. 2011

Arkivoc

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This review discusses strategies for the asymmetric synthesis of sulfoxides, compounds with many applications in stereoselective synthesis and in some cases with pharmaceutical application. The review describes asymmetric oxidation, including metal catalyzed and nonmetal and biological oxidation processes, in addition to synthetic approaches via nucleophilic substitution of appropriately substituted precursors. Kinetic resolution in oxidation of sulfoxides to the analogous sulfones is also discussed; in certain instances, access to enantioenriched sulfoxides can be achieved via a combination of asymmetric sulfide oxidation and complementary kinetic resolution in sulfoxide oxidation.

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“…The presence of an electron-donating group (p-MeO, Entry 5) in 3d [3a] did not appear to effect the reaction or the selectivity. The presence of a conjugated CC bond in cinnamate 3c [5a] led to a slight erosion of diastereoselectivity with alkyne 1a, but not with the bulkier alkyne 1b; in contrast, aliphatic C-substituents at the sulfoximine such as the cyclohexyl derivative 3e [18] were well tolerated. Phenylacetylene 1c reacted in good yield and in excellent diastereoselectivity (Entry 8).…”

mentioning

confidence: 99%

Water-Accelerated Organometallic Chemistry: Alkyne Carboalumination – Sulfinimine Addition and Asymmetric Synthesis of Allylic Amines

Wipf

Nunes

Ribe

2002

HCA

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Dedicated to Professor Dieter Seebach on the occasion of his 65th birthday Carboalumination of alkynes in the presence of catalytic Cp 2 ZrCl 2 and H 2 O affords vinyl-alane intermediates, which serve as nucleophiles in the subsequent addition to enantiomerically enriched (tertbutyl)-and (para-tolyl)sulfinimines. This new in situ protocol produces two new CÀC bonds. Chiral allylic sulfinamides are obtained in high diastereoselectivity and in good yield. Cleavage of the chiral auxiliary leads to synthetically useful allylic amine building blocks, and facile oxidative degradation of the alkene moiety can be used as an approach toward amino acid derivatives and for assignment of absolute configuration.

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Asymmetric synthesis of chiral sulfoxides and sulfinimines by using N-sulfinylsultam

Cited by 50 publications

References 27 publications

Synthesis of Enantiomerically Pure N-tert-Butanesulfinyl Imines (tert-Butanesulfinimines) by the Direct Condensation of tert-Butanesulfinamide with Aldehydes and Ketones

Synthesis of Enantiomerically Pure N-tert-Butanesulfinyl Imines (tert-Butanesulfinimines) by the Direct Condensation of tert-Butanesulfinamide with Aldehydes and Ketones

Synthesis of enantioenriched sulfoxides

Water-Accelerated Organometallic Chemistry: Alkyne Carboalumination – Sulfinimine Addition and Asymmetric Synthesis of Allylic Amines

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