Makoto Emura

A Vibrational Circular Dichroism Approach to the Determination of the Absolute Configurations of Flavorous 5-Substituted-2(5H)-furanones

Sotolon (1) and maple furanone (2) are naturally occurring chiral furanones. These 5-substituted-2(5H)-furanones are industrially significant aroma compounds due to their characteristic organoleptic properties and extraordinarily low odor thresholds. Each enantiomer of 1 and 2 was successfully obtained by preparative enantioselective supercritical fluid chromatography. The absolute configuration of 1 was confirmed as (R)-(-)-1 and (S)-(+)-1 by adopting the vibrational circular dichroism (VCD) approach. The absolute configuration of 2, which has remained ambiguous since its discovery in 1957, was determined as (R)-(+)-2 and (S)-(-)-2 for the first time by the VCD technique. Surprisingly, the signs of the optical rotation of 2 are opposite of those of 1 regardless of their identical absolute configurations. This observation emphasizes the risk in absolute configurational assignments based on comparison of optical rotation signs of similar structures. Odor evaluation of the enantiomers of 2 revealed different odor intensities.

Stereochemical studies of odorous 2-substituted-3(2H)-furanones by vibrational circular dichroism.

Chiral naturally occurring aroma compounds often exhibit enantiomeric excesses due to their stereoselective biogenesis. In general, significant organoleptic differences are perceived between these enantiomers. Chiral 2-substituted-3(2H)-furanones, featuring a unique keto-enol tautomer, the cause of their racemization, have been known to play an important role in flavor because of their extremely low threshold values and their burnt sugar odor characteristics. Since the discovery of these important aroma chemicals, they have been used in large quantities as raw materials in the flavor and fragrance industry. However, absolute configurations of these furanone derivatives have remained ambiguous for the past 40 years. Here optical resolutions of 2,5-dimethyl-4-hydroxy-3(2H)-furanone, 2,5-dimethyl-4-methoxy-3(2H)-furanone, and 4-acetoxy-2,5-dimethyl-3(2H)-furanone were accomplished using chiral CO(2) supercritical fluid chromatography (SFC). Their absolute configurations were unraveled for the first time using the vibrational circular dichroism (VCD) technique as well as by chemical relay reactions. Odor evaluation of each enantiomer revealed relationships between their configurations and odor activities.

Stereochemical study of a novel tautomeric furanone, homofuraneol

A mixture of tautomers with unique keto-enol structures, 5-ethyl-4-hydroxy-2-methylfuran-3(2H)-one and 2-ethyl-4-hydroxy-5-methylfuran-3(2H)-one (EHMF, homofuraneol, 1a and 1b), comprises four structural isomers including their enantiomers. The four isomers were successfully separated by chromatographic optical resolution, and their odor evaluation was performed. Determination of the absolute chemistry of 1a and 1b were accomplished for the first time by direct measurement of the VCD spectra of their methyl ether derivatives 4a and 4b compared with the calculated ones as well as chemical relay reaction. The relationship between odor characteristics and stereochemistry was also examined.

Stereochemical Study of Chiral Tautomeric Flavorous Furanones by Vibrational Circular Dichroism

2-Substituted-3(2H)-furanone derivatives are industrially significant aroma compounds possessing a unique keto-enol tautomeric feature causing their racemization. Absolute configurations of two flavorous furanones, which have remained unclear for the past 40 years since their discovery, were clarified by the vibrational circular dichroism technique as well as chemical relay reactions. Odor evaluation of each enantiomer revealed relationships between their configurations and their odor activities.

The Volatile Constituents of the Coffee Flower (Coffea arabica L.)

Although coffee beans have been well studied, the volatile constituents of the coffee flower have not previously been investigated. An extract of coffee flower (Coffea arabica L.) was analyzed by GC–MS and found to contain a significant number of nitrogen-containing aromatic compounds as well as phenylethane derivatives. The novel epoxygeraniols (2,3-epoxygeraniol and 6,7-epoxygeraniol) were also detected as minor components. These epoxides were estimated to be an approximately equal mixture of both enantiomers by chiral GC analysis. Optically active 2,3-epoxygeraniols were synthesized by Sharplesss asymmetric epoxydation (AE), and 6,7-epoxygeraniols were prepared utilizing Sharplesss asymmetric dihydroxylation (AD) as a key step in high optical purities (96–99% ee). Epoxygeraniols were found to possess rosy and muguet-like aromas reminiscent of the living flower. Considerable differences of aroma were perceived between the enantiomers.