A three-step synthesis of an enantiomerically pure halostachine analogic starting from η6 (o-tolualdehyde)-chromium-tricarbonyl.

doi:10.1016/S0957-4166(00)80208-6

Tetrahedron: Asymmetry

Volume 3, Issue 2, 1992, Pages 287-296

https://doi.org/10.1016/S0957-4166(00)80208-6 Get rights and content

Abstract

An optically pure (+)-S-Halostachine analogue 5a was synthesized in 57% total yield and in three steps from optically pure (−)-aR-[o-tolualdehyde]-chromium-tricarbonyl complex 2b. Various optically pure Halostachine analogues having an ortho-substituted aromatic ring and of both configurations (R and S) are thus available by this route. An X-ray structure of the intermediate complexed oxazoline 3bI allowed to confirm the model we proposed for the approach of a nucleophile on these arene complexes.

References (11)

A. Solladié-Cavallo et al.
Tetrahedron Lett.
(1989)
B.A. Frenz
A. Solladié-Cavallo
U. Schöllkopf
A. Solladié-Cavallo et al.
J. Org. Chim.
(1979)
A. Solladié-Cavallo et al.
Bull. Soc. Chim. Fr.
(1986)
S.G. Davies et al.
J. Chim. Soc.
(1989)

There are more references available in the full text version of this article.

Cited by (16)

3.26 Stoichiometric Auxiliary Ligands for Metals and Main Group Elements: Ligands for Chromium
2012, Comprehensive Chirality
η⁶-(Arene)chromium complexes have seen considerable development for organic synthesis on the basis of the strong electron-withdrawing ability and steric effects of the tricarbonylchromium fragment. The corresponding arene chromium complexes of unsymmetrical 1,2- or 1,3-disubstituted arene ligands are no longer superimposable on their mirror images. Enantiomerically enriched planar chiral arene chromium complexes are accessible by both resolution and asymmetric synthesis. The latter method includes diastereoselective complexation, diastereoselective or enantioselective lithiation/electrophilic quenching, and nucleophilic addition/hydride abstraction. Catalytic asymmetric synthesis of planar chiral arene chromium complexes with chiral catalysts is also described. Planar chiral tricarbonyl(arene)chromium complexes have been widely used in asymmetric synthesis and natural product synthesis, and increasingly as chiral ligands in asymmetric catalysis. This chapter focuses on the synthesis of planar chiral arene chromium complexes and their preparative applications for organic synthesis. Additionally, the synthesis of Fischer-type carbene chromium complexes is briefly described.
Stereoselective reactivity of diastereotopic carbon-carbon triple bonds induced by chiral orthosubstituted arene tricarbonyl chromium complexes. Diastereoselective Co<inf>2</inf>(CO)<inf>8</inf> complexation and LiAlH<inf>4</inf> reduction
1999, Journal of Organometallic Chemistry
A two-step asymmetric synthesis of pure trans-(R,R)-diaryl-epoxides
1996, Tetrahedron Asymmetry
Chromium, molybdenum, and tungsten. Annual survey covering the year 1992
1994, Journal of Organometallic Chemistry
The chemistry of 2-oxazolines (1985-present)
1994, Tetrahedron
2-Oxazolines have permeated numerous sub-disciplines in synthetic organic chemistry in the 100 years since their discovery. This versatile heterocycle has served as protecting group, coordinating ligand, and activating moiety, often exhibiting all of these characteristics in a single transformation. The well-defined reactivity of chiral oxazolines has given rise to numerous highly efficient strategies for asymmetric synthesis including their use as ligands in asymmetric catalysis. Various unique properties have dictated their use in a multitude of dissimilar applications: as monomers in polymer production, as moderators in analytical processes, and as conformationally rigid peptide mimics in medicinal chemistry. Even natural systems have chosen to incorporate oxazolines into their chemical arsenal, as evidenced by the rapidly growing number of identified natural products and their attendant pharmacological properties.
Future studies will undoubtedly uncover unexpected properties and applications. The number of important publications detailing oxazoline-related chemistry is growing, suggesting that research in this area, as in synthetic organic chemistry in general, has yet to mature.
Asymmetric synthesis based on chiral (arene)tricarbonylchromium acetal complexes. Addition reactions to the ortho-formyl complex
2000, Canadian Journal of Chemistry

View all citing articles on Scopus

View full text

A three-step synthesis of an enantiomerically pure halostachine analogic starting from η6 (o-tolualdehyde)-chromium-tricarbonyl.

Abstract

Tetrahedron Lett.

J. Org. Chim.

Bull. Soc. Chim. Fr.

J. Chim. Soc.

A three-step synthesis of an enantiomerically pure halostachine analogic starting from η⁶ (o-tolualdehyde)-chromium-tricarbonyl.