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Synthesis 2011(22): 3592-3603  
DOI: 10.1055/s-0031-1289574
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart ˙ New York

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

Stefan F. Kirsch*a,b, Philipp Klahna,b, Helge Menza
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;
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Publikationsverlauf

Received 9 August 2011
Publikationsdatum:
25. Oktober 2011 (online)

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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

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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.