Organic Reactivity Control by Means of Neighboring Groups and Organometallics. A Personal Account

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Title:Organic Reactivity Control by Means of Neighboring Groups and Organometallics. A Personal Account
Creators:
Kočovský, Pavel
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 59, 1, pp. 1-74

Abstract

<p>This review summarizes the main topics of our research and covers the period of the last 15 years. The prime interest is focused on various ways of controlling the regio- and stereoselectivity of selected organic reactions, in particular electrophilic additions, cleavage of cyclopropane rings, and allylic substitutions by means of neighboring groups and/or transition and non-transition metals. In the first part, the factors governing the course of electrophilic additions are assessed, culminating in the formulation of selection rules for the reactivity of cyclohexene systems, and in a concise synthesis of the natural cardioactive drug, strophanthidin. These studies also contribute to a better understanding of the mechanisms of electrophilic additions. The second part describes recent developments in the stereo- and regiocontrolled cleavage of cyclopropane rings by non-transition metals (Tl and Hg), and the reactivity and transmetalation (with Pd) of the primary products. This methodology has resulted in novel routes to unique polycyclic structures, and will have synthetic applications in the near future. Evidence for the stereospecific "corner" cleavage of the cyclopropane ring has been provided for the first time for Tl and later for Hg. The third part deals with transition metal-catalyzed allylic substitution. Evidence for a new "syn" mechanism for the formation of the intermediate (π-allyl)palladium complex has been provided, which runs counter to the generally accepted "anti" mechanism. A novel method for a Pd-catalyzed allylic oxidation has been developed and employed in the synthesis of natural sesquiterpenes. The increasing importance of transition and non-transition metals for synthetic organic chemistry is demonstrated by their unique reactivity in a number of the papers included in this review.

Title:Organic Reactivity Control by Means of Neighboring Groups and Organometallics. A Personal Account
Creators:
Kočovský, Pavel
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:59
Number:1
Page Range:pp. 1-74
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc19940001UNSPECIFIED
ID Code:419
Item Type:Article
Deposited On:06 Feb 2009 17:00
Last Modified:06 Feb 2009 16:00

Citation

Kočovský, Pavel (1994) Organic Reactivity Control by Means of Neighboring Groups and Organometallics. A Personal Account. Collection of Czechoslovak Chemical Communications, 59 (1). pp. 1-74. ISSN 0010-0765

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