Synthesis and NMR Spectroscopic Elucidation of Four Diastereoisomers of Oxygenated Bisabolane Side Chain

Four possible stereoisomers of a model compound of highly O‐bearing bisabolane sesquiterpenes were synthesized and their NMR spectra were compared. Starting from isopulegol, allylic oxidation and Grignard reaction afforded a mixture of alcohols at C(8), which was separated. After metathesis reaction...

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Veröffentlicht in:	Helvetica chimica acta 2015-08, Vol.98 (8), p.1035-1060
Hauptverfasser:	Hirai, Misaki, Miyazaki, Rurina, Mitsui, Kana, Kiuchi, Kota, Onuki, Hiroyuki, Hirota, Hiroshi, Kuroda, Chiaki
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Sprache:	eng
Schlagworte:	Bisabolanes NMR NMR Spectroscopy Nuclear magnetic resonance Sesquiterpenoids Spectrum analysis Stereochemistry
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creator	Hirai, Misaki Miyazaki, Rurina Mitsui, Kana Kiuchi, Kota Onuki, Hiroyuki Hirota, Hiroshi Kuroda, Chiaki
description	Four possible stereoisomers of a model compound of highly O‐bearing bisabolane sesquiterpenes were synthesized and their NMR spectra were compared. Starting from isopulegol, allylic oxidation and Grignard reaction afforded a mixture of alcohols at C(8), which was separated. After metathesis reaction, both α‐ and β‐epoxides were obtained via non‐stereoselective epoxidation, while VO(OiPr)3‐catalyzed epoxidation afforded a single diastereoisomer selectively. NMR Spectra of twelve synthesized compounds, four stereoisomers of acetates, isobutyrates, and tiglates, were measured. A difference between C(8α)‐ and C(8β)‐acyloxy isomers was observed in the δ‐values of HC(8) in CDCl3. Within the 8β‐acyloxy compounds, the α‐ and the β‐epoxides were distinguished by either the J‐value of HC(8) or the chemical shift of CH2(9). Within the 8α‐acyloxy compounds, two epoxide isomers were distinguished by the J‐value of HC(10) in C6D6 or in CD3OD.
doi_str_mv	10.1002/hlca.201400395
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Starting from isopulegol, allylic oxidation and Grignard reaction afforded a mixture of alcohols at C(8), which was separated. After metathesis reaction, both α‐ and β‐epoxides were obtained via non‐stereoselective epoxidation, while VO(OiPr)3‐catalyzed epoxidation afforded a single diastereoisomer selectively. NMR Spectra of twelve synthesized compounds, four stereoisomers of acetates, isobutyrates, and tiglates, were measured. A difference between C(8α)‐ and C(8β)‐acyloxy isomers was observed in the δ‐values of HC(8) in CDCl3. Within the 8β‐acyloxy compounds, the α‐ and the β‐epoxides were distinguished by either the J‐value of HC(8) or the chemical shift of CH2(9). Within the 8α‐acyloxy compounds, two epoxide isomers were distinguished by the J‐value of HC(10) in C6D6 or in CD3OD.</abstract><cop>Zürich</cop><pub>WILEY-VCH Verlag</pub><doi>10.1002/hlca.201400395</doi><tpages>26</tpages></addata></record>
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subjects	Bisabolanes NMR NMR Spectroscopy Nuclear magnetic resonance Sesquiterpenoids Spectrum analysis Stereochemistry
title	Synthesis and NMR Spectroscopic Elucidation of Four Diastereoisomers of Oxygenated Bisabolane Side Chain
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