A Chemoenzymatic, Preparative Synthesis of the Isomeric Forms of p‐Menth‐1‐en‐9‐ol: Application to the Synthesis of the Isomeric Forms of the Cooling Agent 1‐Hydroxy‐2,9‐cineole

Abstract

A preparative-scale synthesis of the four p-menth-1-en-9-ol isomers 2a-5a has been achieved by means of two chemoenzymatic processes. Both synthetic pathways start from the enantiomeric forms of limonene that are converted into p-mentha-1,8-dien-9-al isomers 12 and 15. The baker's yeast mediated reduction of the latter aldehydes afforded compounds 3a and 5a, respectively, with very high enantioselectivity. Moreover, chemical reduction of 12 and 15 gives the mixtures of enantiopure diastereoisomers 2a/3a and 4a/5a,

Saccharomyces cerevisiae: a potential stereospecific reduction tool for biotransformation of mono‐ and sesquiterpenoids

“…Limonene and its derivatives are enantiopure starting materials commonly used as precursors for the synthesis of other useful compounds, due to their inexpensiveness and vast availability. Serra and co‐workers98 synthetically converted both enantiomeric forms of limonene into aldehyde p ‐mentha‐1,8‐dien‐9‐al isomers, subsequently reducing the conjugated double bonds into their respective alcohols utilizing baker's yeast. High percentage diastereomeric excesses (96% and 97%) were obtained with good yields, and a new chiral centre formed has high preference for the ( R ) absolute configuration.…”

Regio‐ and Stereoselective Synthesis of Bicyclic Limonene‐Based Chiral Aminodiols and Spirooxazolidines

“…(S)-Isoperillyl alcohol (2), (S)-p-mentha-1,8-dien-9-al (3), (S)-p-mentha-1,8-dien-9-oic acid (4), and (1S,5S)-4-methyl-7-methylenebicyclo[3.2.1]oct-3-en-6-one (5) were prepared according to literature procedures, and all spectroscopic data were similar to those reported. [28,34] (1S,5S,6R)-4-Methyl-7-methylenebicyclo[3.2.1]oct-3-en-6-ol (6):A suspension of NaBH 4 (1.5 g, 39.65 mmol) in MeOH (21 mL) was added dropwise to an ice-cold solution of 5 (1.5 g, 10.12 mmol) in MeOH (18 mL). Stirring was continued for 4h at 0 8C.…”

“…ation to afford allylic alcohol 2. [28][29][30] The resulting allylic alcohol was oxidized to aldehyde 3, [28] which was then converted into carboxylic acid 4 by applying aliterature method. [31][32][33][34] Intramolecular acylation of isoperillic acid(4), performed by using earlier methods, [34,35] resulted in bicyclic methylene ketone 5 as a single product ( Figure 1).…”

Curcuma longa and Curcuma mangga leaves exhibit functional food property

“…Based on the spectral data, compound 6 was characterized as menth-1-en-9-ol (Serra, Fuganti, & Gatti, 2008 C-1, 7), 39.8 (C-2, 6), 43.0 (C-4), 54.4 (OMe), 69.0 (C-3, 5), 111.2 (C-5 0 , 5 00 ), 114.2 (C-2 0 , 2 00 ), 119.9 (C-6 0 , 6 00 ), 133.3 (C-1 0 , 1 00 ), 143.6 (C-4 0 , 4 00 ), and 146.9 (C-3 0 ,3 00 ). From the spectral data, compound 7 was identified as octahydrocurcumin (Ohtsu et al, 2002).…”