Organic chemists have always been fascinated by the cyclopropane subunit.1 The smallest cycloalkane is found as a basic structural element in a wide range of naturally occurring compounds.2 Moreover, many cyclopropane-containing unnatural products have been prepared to test the bonding features of this class of highly strained cycloalkanes3 and to study enzyme mechanism or inhibition.4 Cyclopropanes have also been used as versatile synthetic intermediates in the synthesis of more functionalized cycloalkanes5,6 and acyclic compounds.7 In recent years, most of the synthetic efforts have focused on the enantioselective synthesis of cyclopropanes.8 This has remained a challenge ever since it was found that the members of the pyrethroid class of compounds were effective insecticides.9 New and more efficient methods for the preparation of these entities in enantiomerically pure form are still evolving, and this review will focus mainly on the new methods that have appeared in the literature since 1989. It will elaborate on only three types of stereoselective cyclopropanation reactions from olefins: the halomethylmetal-mediated cyclopropanation reactions (eq 1), the transition metal-catalyzed decomposition of diazo compounds (eq 2), and the nucleophilic addition-ring closure sequence (eqs 3 and 4). These three processes will be examined in the context of diastereoand enantiocontrol. In the last section of the review, other methods commonly used to make chiral, nonracemic cyclopropanes will be briefly outlined.

Stereoselective Cyclopropanation Reactions

Publisher Summary This chapter discusses prostaglandins and thromboxanes. The prostaglandins are C 20 acids formed from polyunsaturated fatty acids by oxygenation and cyclization. The thromboxanes, which were originally found in platelets, have now been identified in a variety of tissues. Rapid progress is being made in understanding their biological roles. Earlier studies on vascular and airway smooth muscle demonstrated that endoperoxides had unique effects that could not be attributed to conversion into the stable prostaglandins. Because aspirin, an inhibitor of endoperoxide formation, inhibits the second wave of aggregation, it was suggested that the endoperoxides play a role in the release reaction. The potency of the endoperoxides in causing contractions of the isolated rabbit aorta was of particular interest. However, the occurrence of thromboxanes is not limited to platelets. The transformation of arachidonic acid into thromboxane B 2 has also been observed in lung tissue, spleen, kidney, leukocytes, umbilical artery, and brain.

Prostaglandins and thromboxanes.

On the origins of triterpenoid skeletal diversity.

Free radical formation by antitumor quinones

During the final larval instar of the tobacco hornworm the presence of juvenile hormone (JH) inhibits the secretion of the brain9s prothoracicotropic hormone (PTTH). The corpora allata cease to secrete JH when the larvae attain a weight of approximately 5 g. The JH is cleared from the haemolymph in about 24 h. This process in itself renders the brain competent to release PTTH. The actual release of PTTH occurs at the very first photo-periodic gate after the JH has disappeared from the haemolymph. A functional failure of this normal mechanism is apparently responsible for the developmental standstill of Lepidoptera which diapause as mature larvae.

Masanao Matsui

Papers

Mitomycin derivatives. 1. Preparation of mitosane and mitosene compounds and their biological activities.

Total synthesis of stevioside

Diterpenoid total synthesis—XIX : (±)-Steviol and erythroxydiol A: Rearrangements in bicyclooctane compounds

Synthesis of compounds with juvenile hormone activity—XI

Stereoselective synthesis of optically active disparlure, the pheromone of the gypsy moth (Porthetria dispar L.)