Partial Syntheses of Methyl Dehydrojasmonate and Tuberolactone

Abstract

SummaryThe natural products methyl dehydrojasmonate (1) and tuberolactone (2) have been synthesized from methyl jasmonate (3) and jasmolactone (4) resp., via sulfenylation-sulfoxide pyrolysis. Although no pertinent organoleptic data are available, these compounds were assumed to be of special olfactive importance. Moreover, they exhibit close structural relationships to the well known, olfactively interesting com- These results were reported by P. Dubs at the Autumn session of the Swiss Chemical Society

A One Pot Synthesis of Dehydrohedione (DHH) from a Hedione® Precursor

“…We thus similarly applied the Kochi 's methodology to 2a ,, and, to our delight, we obtained directly and cleanly, in a one pot, DHH 1a . This domino reaction, constitutes the shortest synthesis of 1a , thus avoiding trans ‐ Hedione ® 6a as a starting material for either halogenation/dehydrohalogenation,, or enol acetate formation/epoxidation/rearrangement, or HIO 3 oxidation,, , as key intermediate for the final hydrogenation towards the olfactively more appreciated cis ‐ Hedione ® 6b , or its even more powerful enantiomer (+)‐(1 R ,2 S )‐ cis ‐ 6b , named Paradisone ® ,…”

“…[17] We thus similarly applied the Kochi's methodology to 2a, [17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33], 3 and, to our delight, we obtained directly and cleanly, in a one pot, DHH 1a. This domino reaction, constitutes the shortest synthesis of 1a, thus avoiding trans-Hedione â 6a as a starting material for either halogenation/dehydrohalogenation, [31][33] [34],4 1 For the diethyl 2-(3-oxo-2-pentylcyclopentyl)malonate analogue, see. [6 -10] 2 The demethoxycarbonylated intermediate 4b (LiBr, DMF, 80°C, 81% yield from 4a), was earlier obtained, besides 1a, by addition of Me-diazoacetate to 5a, followed by thermal extrusion of N 2 at 230°C, while subsequent Birch reduction afforded trans-Hedione â 6a [14] (6a is always containing ca.…”