The Use of COP-OAc
in the Catalyst-Controlled Syntheses of 1,3-Polyols

Stefan F. Kirsch; Philipp Klahn; Helge Menz

doi:10.1055/s-0031-1289574

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Synthesis 2011(22): 3592-3603
DOI: 10.1055/s-0031-1289574

FEATUREARTICLE

The Use of COP-OAc in the Catalyst-Controlled Syntheses of 1,3-Polyols

Stefan F. Kirsch*^a,b, Philipp Klahn^a,b, Helge Menz^a
^a Department Chemie, Technische Universität München, Lichtenbergstr. 4, 85747 Garching, Germany
Fax: +49(89)28913315; e-Mail: stefan.kirsch@ch.tum.de;
^b Bergische Universität Wuppertal, Fachbereich C - Organische Chemie, Gaußstraße 20, 42119 Wuppertal, Germany
e-Mail: sfkirsch@uni-wuppertal.de;

Further Information

Publication History

Received 9 August 2011
Publication Date:
25 October 2011 (online)

Abstract
Full Text
References
Supplementary Material

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Abstract

An iterative strategy to the 1,3-polyol motif is described. The use of the catalytic asymmetric Overman esterification for the construction of all stereogenic centers is broadly examined as are the sequences to extend the developing polyol chain. The iterative strategies are applied to the total syntheses of rugulactone and polyrhacitides A and B.

1 Introduction

2 Results and Discussion

2.1 Chain Elongation via RCM (Cycle A)

2.2 Total Synthesis of Rugulactone

2.3 Chain Elongation via Ando Olefination (Cycle B) and Total Syntheses of Polyrhacitides A and B

2.4 Useful Variants

3 Conclusions

Key words

polyols - palladium - catalysis - natural products - esters

Supporting Information

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34

It should be mentioned that the use of triethylsilyl protecting groups does not show these deprotection issues, see: ref. 24.

38

It has to be noted that the isolation of aldehyde 16 is somewhat troublesome, and, therefore, it is recommended to use it without further purification (see ref. 36d). Nevertheless, 16 can be isolated and stored at -20 ˚C over weeks without decomposition. See the experimental section and the Supporting Information for analytical data.

Supplementary Material

Supporting Information