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Volume 48, Issue 27
Pages 5579-5586

PII: S0040-4020(01)90135-8
Copyright © 1992 Published by Elsevier Science Ltd. All rights reserved.

Investigation of the diastereofacial selectivity of the addition of 1-metalated (E)- and (Z)-hept-1-enes to the COREY aldehyde - a comparison between vinyllithium and vinyltitanium compounds*1, *2

H. Schick, *, J. Spanig, R. Mahrwald, M. Bohle and T. Reiher

K. K. Pivnitsky

Central Institute of Organic Chemistry, Rudower Chaussee 5, D(0)-1199 Berlin-Adlershof, Federal Republic of Germany
All-Russian Endocrinological Scientific Centre of the Russian Academy of Medical Sciences, Institute of Experimental Endocrinology, ul. Moskvorech'e 1, 115 522 Moscow, Russia

Received 3 February 1992.  Available online 8 March 2001.


In connection with the synthesis of prostaglandin intermediates a comparison of the addition of (Z)- and (E)-hept-1-enyllithium and (Z)- and (E)-hept-1-enyltitanium triisopropoxide to the COREY aldehyde revealed that the lithium compounds are preferentially added by a si-attack, the titanium compounds, however, by a preferred re-attack. The diastereoselectivity of the lithium compounds was generally better than that of the titanium analogues. This result is explained by assuming a different chelation tendency of the metals. Molecular mechanics calculations support this interpretation.

Graphical Abstract

Vinyllithium compounds add with higher diastereoselectivity to the COREY aldehyde than the corresponding vinyltitanium compounds affording intermediates for (15R)-prostaglandins:



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*1 Prostaglandins and Prostaglandin Intermediates, 28. For part 27 see ref. 7.

*2 Part of the Thesis of J. Spanig, Friedrich-Schiller-Universität Jena, 1991.

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