Syntheses of Natural(+)-Juvabione, Its Enantiomer(-)-Juvabione, and Their Diastereoisomers (+)- and (-)-Epijuvabione

Abstract

The insect juvenile hormone, (+)-juvabione (la), has been synthesized from (+)-(4R,8/?)-/>-menth-len-9-ol, obtained by hydroboration of (ft)-(+)-limonene, via (2S)-[4-methyl-3-cyclohexen-(l/?)-yl]-6-methylheptan-4-one (10). Two routes for the oxidation of the allylic methyl group of 10, photochemical oxygenation and formation and opening of an oxirane via ß elimination, are described. This work establishes the absolute stereochemistry of la as R,S at the two asymmetric centers, in contradiction to the previously deduced R,R configuration. Syntheses of (-)-juvabione (3a), (+)-epijuvabione (4a), and (-)-epijuvabione ( 5) are also reported. The four diastereoisomers were very similar in all physical properties, except optical rotatory dispersion and circular dichroism which showed striking differences. These data are discussed.(11) J. F. Blount, B. A. Pawson, and G. Saucy, ibid., 715, 1016 (1969).(12) The absolute stereochemistry of (+)-todomatuic acid had been assigned5 based upon comparisons of the molecular rotations ([M]d) of the acid and its conversion products with sesquiterpenes of known absolute stereochemistry.

Insect juvenile hormones and their bioanalogues

“…23 The originally published 19 ,20 absolute configuration of juvabione and dehydrojuvabione was soon revised. 24 and Evans and Nelson. 29 Further research dealing with substances present in the wood of balsam fir was not unfertile either.…”

Readily Available Chiral Carbon Fragments and Their Use in Synthesis

“…We therefore note the preparation (Scheme 86) of the juvenile hormones juvabione (1154) (477) and juvabiol (1155) (478) and the defensive secretions chrysomelidial (1156) and plagiolactone (1157) (479), all from (/?)-limonene. Mori (91) devised a stereoselective synthesis of both enantiomers of this compound, starting from the appropriate tartaric acids.…”

Synthese eines 17β‐homologen 3β‐Hydroxy‐card‐5,22‐dienolids Partialsynthetische Versuche in der Reihe der Herzgifte, 8. Mitteilung

“…1)ie Chroinatographie konntc im L X . -5-en-21-nitriZ (10) aus 9 (nach [8]). Die Losung von 10,55 g (19,42 mmol) 9 in 262 ml wasserfreiem DMSO wurde unter Nz (durch Waschen mit konzentrierter Schwefelsaure von Feuchtigkeit befreit) auf 90" erhitzt, 3,67 g (73,5 mmol) Natriumcyanid (5 Std.…”

“…1.51). Durch Reduktion der Esterfunktion von 7 rnit Lithiumaluminiumliydrid [6] konnte zu 97% 38-[ (Tetrahydro-2' H-pyran-2'-yl)oxy] androst-5-en-17Bmethanol (8) gewonnen werden. Veresterung der primaren Hydroxylgruppe von 8 rnit $-Toluolsulfosaure 171 ergab 3~-~(Tetraliydro-2'H-pyran-2'-yl)oxy~-17~-[(tosyloxy)methyl]androst-5-en (9).…”