Determination of the absolute configuration of secondary alcohols by modified Horeau's method using HPLC

Abstract

A method for determination of absolute configuration of secondary alcohols, based on a modified Horeau's method, has been developed. The ratio of (1R,2'S)- and (1R,2'R)-N-[1-(1-naphthyl)-ethyl]-2-phenylbutanamides (V and VI, respectively) was determined by HPLC on a straight phase. The method was tested on a series of steroid and terpene model compounds and was used in the determination of absolute configuration of 15-ripperten-3α-ol (XV), the defense substance of Nasutitermes nigriceps termites. The sensibility of the determination is 100 nmol of the alcohol.

New Trichothecenes Isolated from Holarrhena floribunda

“…15 The stereochemistry of 6 was assigned by the NOESY spectrum in conjunction with the determination of absolute configuration at C-3 by modified Horeau's method using HPLC. 16 Reaction of 6 with racemic 2-phenylbutanoic anhydride, followed by addition of (R)-(+)-1-(1-naphthyl)ethylamine afforded a mixture of (1R,2′S)-and (1R,2′R)-N-[1-(1-naphthyl)ethyl]-2-phenylbutanamides, in the proportion of 69:31 as calculated by HPLC (Table 3), which is indicative of an R configuration of the secondary hydroxy group of 6.…”

“…1 H (400 MHz) and 13 C (100.61 MHz) 1D and 2D NMR spectra were recorded on a Bruker ARX-400 spectrometer. Determination of absolute configuration by modified Horeau's method using HPLC 16 was carried out on a Spectra Physics 100 chromatograph, equipped with a UV detector and a Nucleosil-100 column (5 µm, 25 cm × 4.6 mm i.d.). The following Merck chromatographic supports were used: Si gel, 230-400 mesh, and LiChroprep RP18, 40-63 µm, for flash and reversed-phase column chromatography, respectively; Si gel plates, 0.25 and 2 mm thick, for analytical and preparative HPTLC, respectively; HPTLC DIOL F254S plates, 0.2 mm thick; and RP18 F254S plates, 0.25 mm thick.…”

Chromatographic Determination of the Absolute Configuration of an Acyclic Secondary Alcohol Using Difluorodinitrobenzene

“…To our knowledge, there is only one method using HPLC, the modified Horeau method, 15 for the determination of the absolute configuration of a chiral secondary alcohol. This method relies on the kinetic resolution of racemic 2-phenylbutyric anhydride by the chiral secondary alcohol.…”