Asymmetric sharpless epoxidation of divinylcarbinol. Erythro-D- and -L-4-pentenitols by hydrolysis of regioisomeric epoxy-4-pentenols

doi:10.1016/S0040-4020(01)96130-7

Tetrahedron

Volume 47, Issues 12–13, 1991, Pages 2195-2210

https://doi.org/10.1016/S0040-4020(01)96130-7 Get rights and content

Abstract

The asymmetric Sharpless epoxidation of divinylcarbinol (1), a secondary, achiral allylic alcohol, is described in detail. The epoxidation proceeds with high enantio-control and diastereo-selection. The resulting 1,2-epoxy-4-pentene-3-ols 2 are equilibrated to afford the internal epoxides 5. Hydrolysis of the regioisomers 2 and 5, respectively, furnishes opposite enantiomers of erythro-4-pentenitols 3 with high selectivity. Several derivatives of 3 are described, as well as results of a less stereoselective route - from D-glyceraldehyde acetonide (10) - providing NMR data of the threo series. -The acute toxicity of divinylcarbinol (1) is reported, along with the mutagenicity of 1, L-2 and L-5 as determined by Ames tests.

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Citation Excerpt :
So, β-hydroxy sulfides have been used for the synthesis of allylalcohols,1 cyclic sulfides,2 thioketones,3 a number of important natural products,4 and a variety of compounds with pharmacological and/or biological activity.5 In general, the thiolysis of epoxides is achieved by using thiolates under basic conditions5c,6 or with thiols in the presence of some activating agent.7 Although some of these methods afforded β-hydroxy sulfides with high regioselectivity7j,k an alternative synthesis of enantiopure β-hydroxy sulfides with complete selectivity, in which different diastereoisomers could be available, would be still desirable.

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^☆: a) Part of the Dissertation of D. Schröter, Universität Würzburg, 1990. - b) The concept of this work was first presented at the Xth International Congress of Heterocyclic Chemistry, Waterloo/Canada, August 1985, see Ref. 8–10.

^☆☆: a) Preliminary communication: Häfele, B.; Schröter, D.; Jäger, V. Angew. Chem. 1986, 98. 89; Angew. Chem. Int. Ed. Engl. 1986, 25, 87. - b) CGC analyses on chiral stationary phases: Koppenhoefer, B.; Walser, M.; Schröter, D.; Häfele, B.; Jäger, V. Tetrahedron 1987. 43, 2059.

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Asymmetric sharpless epoxidation of divinylcarbinol. Erythro-D- and -L-4-pentenitols by hydrolysis of regioisomeric epoxy-4-pentenols☆,☆☆

Abstract

Org. Synth.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

Pure Appl. Chem.

Aldrichim. Acta

Modern Synthetic Methods

Angew. Chem.

Synthesis

Nachr. Chem. Tech. Lab.

Tetrahedron Lett.

Helv. Chim. Acta

Can. J. Chem.

J. Org. Chem.

J. Org. Chem.

Angew. Chem.

J. Org. Chem.

J. Org. Chem.

J. Am. Chem. Soc.

Tetrahedron Lett.

Tetrahedron Lett.

Synthesis

Synthesis

J. Org. Chem.

J. Am. Chem. Soc.

Tetrahedron Lett.

Helv. Chim. Acta

Synthesis

Lect. Heterocycl. Chem.

Studies in Organic Chemistry

J. Chem. Soc.

J. Am. Chem. Soc.

C. R. Acad. Sci.

Carbohydr. Res.

Helv. Chim. Acta

Tetrahedron Lett.

Tetrahedron Lett.

Tetrahedron Lett.

J. Am. Chem. Soc.

Angew. Chem.

J. Org. Chem.

Tetrahedron Lett.

Tetrahedron Lett.

Tetrahedron Lett.

Tetrahedron Lett.

Tetrahedron Lett.

22. GdChHauptversammlung

Angew. Chem.

J. Org. Chem.

Synthesis

Ann. Chim.

J. Org. Chem.

J. Org. Chem.

J. Org. Chem.

Dissertation

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J. Am. Chem. Soc.

Tetrahedron

J. Chem. Soc.

Q. Rev. Chem. Soc.