Asymmetric Synthesis and Properties of Sulfinimines (Thiooxime S-Oxides)
- 1 April 1997
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 62 (8) , 2555-2563
- https://doi.org/10.1021/jo970077e
Abstract
Enantiomerically pure sulfinimines (thiooxime S-oxides 10), important building blocks in the asymmetric synthesis of amine derivatives, are prepared in good to excellent yields in one step from aromatic, heteroaromatic, and aliphatic aldehydes. This protocol involves treating commercially available (R)- or (S)-menthyl p-toluenesufinate (Andersen reagent 4) with LiHMDS, followed by the aldehyde, affording (E)-10 exclusively. The sulfinimines 10 are formed via a Peterson-type olefination reaction of silylsulfinamide anion 13 with the aldehyde. Anion 13 is generated by reaction of lithium menthoxide (12a) with bis(trimethylsilyl)sulfinamide 11, which is formed in the reaction of 4 with LiHMDS. The other product formed is O-(trimethylsilyl)menthol (12c), which is isolated in >80% yield for recycling. Two other less efficient methods for the asymmetric synthesis of 10 are discussed: (i) the asymmetric oxidation of sulfenimines 6 with chiral nonracemic oxaziridines and (ii) the reaction of metal aldimines, prepared from nitriles, with 4. All of these protocols fail with ketones.Keywords
This publication has 46 references indexed in Scilit:
- Asymmetric Strecker Synthesis Using Enantiopure Sulfinimines and Diethylaluminum Cyanide: The Alcohol EffectThe Journal of Organic Chemistry, 1996
- An Efficient Synthesis of (S)-(+)-Ethyl β-Amino-3-pyridinepropanoate Using Enantiopure SulfiniminesThe Journal of Organic Chemistry, 1996
- Asymmetric Synthesis of (R)-(+)-.beta.-Phenylalanine from (S)-(+)-Benzylidene-p-toluenesulfinamide. Regeneration of the Sulfinimine PrecursorThe Journal of Organic Chemistry, 1995
- Application of New Camphor-Derived Mercapto Chiral Auxiliaries to the Synthesis of Optically Active Primary AminesThe Journal of Organic Chemistry, 1994
- Chemistry of sulfenic acids. 7. Reason for the high reactivity of sulfenic acids. Stabilization by intramolecular hydrogen bonding and electronegativity effectsThe Journal of Organic Chemistry, 1986
- A Novel Synthesis of Arenesulfinamides fromS-4-NitrophenylS-Substituted-Phenyl Sulfoximides with Elemental Sulfur in Liquid AmmoniaSynthesis, 1983
- Direct conversion of nitriles to .alpha.-alkylated aldehydesThe Journal of Organic Chemistry, 1981
- Chemistry of the sulfur-nitrogen bond. 14. Arenesulfenic acids from N-alkylidenearenesulfinamides (sulfinimines)Journal of the American Chemical Society, 1978
- Chemistry of the sulfur-nitrogen bond. X. Barriers to planar inversion in N-(4,4'-dimethylbenzophenylidene)arenesulfenamides and -selenenamidesJournal of the American Chemical Society, 1976
- Derivatives of Aromatic Sulfinic Acids. II. The Reaction of Thionyl Chloride with Sulfinic Esters1,2Journal of the American Chemical Society, 1956