Absolute Configuration and Optical Rotatory Power of Sulfoxides and Sulfinate Esters^1,2

Abstract

thoroughly extracted with 6 N hydrochloric acid, the acidic extract was made strongly alkaline by addition of potassium carbonate, and this basic solution was extracted with ether. After drying with anhydrous magnesium sulfate the ether was carefully distilled off leaving a small quantity (ca. 200 mg.) of a white crystalline material with an infrared spectrum identical with that of urethan.In a similar irradiation of a more concentrated solution of I in cyclohexane (1:10 M ratio) a small amount of diethyl hydrazodiformate (IX) was found.Attempted Radical-Initiated Decomposition of Ethyl Azidoformate in Cyclohexane. In a water bath of 49 ± 1°, a solution of 1.060 g. (9 X 10-3 mole) of redistilled ethyl azidoformate in 125 ml. of purified cyclohexane was placed in the flask, and the system was flushed with purified nitrogen and then sealed. A total of about 1.8 X 10-2 moles of diethyl peroxydi-carbonate67 was injected in portions over a 4-day period producing a slow evolution of an unidentified gas; the volume evolved at various intervals is re-(4) R.

The oxidation of organic sulphides by Mortierellaisabellina. 2. Effects of substituents on the stereochemistry of sulphoxide formation

“…It therefore seems likely that, in the case of sulphone formation from 2g and 2j, both oxidations occur without the substrate leaving the enzyme's active site; it may therefore not be possible to directly determine the stereoselectivity of the second oxidation. The assignment of absolute.stereochemistry to the predominant sulphoxide enantiomers in Table 1 follows from the results reported for the absolute stereochemistry of alkyl aryl sulphoxides of known optical rotation (14,15,19,20).…”

“…Our estimate of optical purity for the sulphoxide 1 b differs from that previously reported by Sih and co-workers (8) for 1 b obtained from the same fungus. The latter group, however, estimated their optical purity solely from rotation measurements; at least three different values for the specific rotation of ( R ) -l b appear in the literature (6,15). The values reported in Table 1 for the enantiomeric enrichment of sulphoxides 2g and 2 j may not be directly attributable to stereospecific sulphide oxidation.…”

The crystal structure and absolute configuration of (+)-methyl-p-tolyl sulfoxide

“…At the time this study was started the conversion of (-)-p-tolyl (-)-menthyl sulfinate (I) to (+)-methyl p-tolyl sulfoxide (II) by treatment with methyl Grignard reagent was thought to proceed via inversion of configuration, based on optical rotatory dispersion and circular dichroism studies by Mislow, Green, Lauer, Melillo, Simmons & Ternay (1965). …”

Asymmetric Synthesis of α-Substituted-β-Amino Phosphonates and Phosphinates and β-Amino Sulfur Analogs

“…A correlation exists between the absolute configuration of sulfinyl derivatives and their chiroptical properties, 61 whose chirality has allowed the extention of the synthetic utility of the sulfinyl group to the field of asymmetric synthesis.…”