Elsevier

Tetrahedron

Volume 60, Issue 23, 31 May 2004, Pages 5013-5017
Tetrahedron

Grob-type fragmentation of a carvone derived β-hydroxymesylate: application to the synthesis of chiral lavandulol derivatives

https://doi.org/10.1016/j.tet.2004.04.023Get rights and content

Abstract

Grob-type fragmentation of the carvone derived diol-monosulphonate 5 has been utilised for the enantioselective synthesis of various lavandulol derivatives

Introduction

Although the cyclic template of the monoterpene carvone has been extensively utilised as a chiral-pool material for the asymmetric synthesis of diverse cyclic structures of interest, its application in the synthesis of acyclic chiral molecules is somewhat less documented.1 During the course of our studies2 towards the construction of taxoids from carvone, we were attracted to the possibility of developing new routes to some acyclic chiral molecules of interest from carvone using suitable ring-opening protocol. Herein, we describe our efforts towards the synthesis of various chiral lavandulol derivatives from carvone. Our strategy relied on the identification of the stereogenic center at C-5 of carvone as identical to that of lavandulol at C-2 and some restructuring plans for the synthesis of various lavandulol derivatives could also be envisioned (Fig. 1).

Section snippets

Results and discussion

Our synthetic approach commenced from the cheaper, more abundant R(−)-carvone (1) which was readily elaborated to the hydroxyketone 3 via a two step sequence involving reductive methylation of the derived epoxyketone 2 as described previously.3 In line with our earlier observation,2 addition of methylmagnesium iodide to 3 proceeded with high diastereoselectivity and the diol 4 was obtained in good yield after removal of the minor isomer (5%). Selective mesylation of the secondary hydroxy group

Conclusion

In short, we have demonstrated that various chiral lavandulol derivatives could be prepared from carvone through a fragmentation-based approach. Some of the compounds reported here have the potential to find applications in perfumery.

General details

Optical rotations were recorded in spectroscopic grade chloroform or dichloromethane on a Jasco DIP-370 polarimeter, [α]D values are recorded in units of 10−1 deg cm2 g−1. Infrared spectra were obtained using a Perkin–Elmer 1600 series spectrometer as liquid films or dilute solutions in spectroscopic grade dichloromethane. Proton NMR spectra were recorded on a Bruker DRX-300 spectrometer as dilute solutions in deuterochloroform. The chemical shifts are quoted in parts per million (ppm) relative to

Acknowledgements

Financial assistance from the CSIR, New Delhi (Grant No. 00/EMR/II-1676) is gratefully acknowledged.

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