37841-91-1

Usage

Uses

Isovelleral is an irritant fungal terpenoid that inhibits the TRPV1 channel.

InChI:InChI=1/C15H20O2/c1-13(2)5-10-4-11(7-16)15(9-17)8-14(15,3)12(10)6-13/h4,7,9-10,12H,5-6,8H2,1-3H3/t10-,12+,14-,15-/m1/s1

Upstream product

• 135024-80-5 C₁₆H₂₄O₃ 
• 336102-07-9 (4aS,5S)-5-{[tert-butyl(dimethyl)silyl]oxy}-4a,7,7-trimethyl-4,4,a,5,6,7,8-hexahydro-2(3H)-naphthalenone 
• 336102-09-1 (3R,4aS,5S)-3-allyl-5-{[tert-butyl(dimethyl)silyl]oxy}-4a,7,7-trimethyloctahydro-2(1H)-naphthalenone 
• 94061-53-7 C₁₆H₂₄O₃ 
• 130543-20-3 (4,4-Dimethyl-cyclopent-1-enylmethyl)-triphenyl-phosphonium; bromide 
• 82351-48-2 ethyl trans-4,4-dimethyl-6-oxo-2-hexenoate 
• 5497-67-6 2,2-dimethyl-4-pentenal 

Downstream Products

• 109956-89-0 iso-isovelleral 
• 131434-67-8 <3aS-(3aα,6β,8aα)>-1,2,3,3a,6,7,8,8a-octahydro-2,2-dimethyl-8-methylene-5,6-azulenedicarboxaldehyde 
• 131367-58-3 <3aS-(3aα,6α,8aα)>-1,2,3,3a,6,7,8,8a-octahydro-2,2-dimethyl-8-methylene-5,6-azulenedicarboxaldehyde 
• 96910-70-2 isovellerol 
• 37841-93-3 ((1aS,3aS,6aS,6bR)-2-(hydroxymethyl)-5,5,6b-trimethyl-3a,4,5,6,6a,6b-hexadrocyclopropa[e]inden-1a(1H)-yl)methanol 

Relevant academic research and scientific papers

A novel route to the marasmane skeleton via a tandem rearrangement-cyclopropanation reaction. Total synthesis of (+)-isovelleral

A general and efficient route to the marasmane skeleton is described. Total syntheses of two simple marasmanes (35 and 37) in racemic form were achieved using a MgI2-catalyzed rearrangement-cyclopropanation reaction of trimethylsilyl enol ether 31 derived from naphthalenone 30. The reaction proceeds in high yield with complete diastereoselectivity and does not require the use of special cyclopropanation reagents. Application of this novel route to the marasmane framework was extended to the synthesis of naturally occurring (+)-isovelleral (41).

STUDIES OF THE CONVERSIONS OF SESQUITERPENES IN INJURED FRUIT BODIES OF LACTARIUS VELLEREUS. A BIOMIMETIC TRANSFORMATION OF STEAROYLVELUTINAL TO ISOVELLERAL.

An intermediate in the conversion of stearoylvelutinal to the antibiotic unsaturated dialdehyde isovelleral in injured fruit bodies of Lactarius vellereus is proposed.Further insight in the enzymatic conversions of sesquiterpenes in this species was obtained by feeding experiments with isovelleral labelled with (2)H.

A Carbene Catalysis Strategy for the Synthesis of Protoilludane Natural Products

The Armillaria and Lactarius genera of fungi produce the antimicrobial and cytotoxic mellolide, protoilludane, and marasmane sesquiterpenoids. We report a unified synthetic strategy to access the protoilludane, mellolide, and marasmane families of natural products. The key features of these syntheses are 1) the organocatalytic, enantioselective construction of key chiral intermediates from a simple achiral precursor, 2) the utility of a key 1,2-cyclobutanediol intermediate to serve as a precursor to each natural product class, and 3) a direct chemical conversion of a protoilludane to a marasmane through serendipitous ring contraction, which provides experimental support for their proposed biosynthetic relationships.

The Thermal Isomerization of the Sesquiterpenes Isovelleral and Merulidial. A Reversible Ring Opening of the cis-Methylcyclopropanecarbaldehyde Group via an Intramolecular Ene Reaction

Fungal sesquiterpene dialdehydes of marasmane and isolactarane types, such as isovelleral (1) and merulidial (7), undergo a reversible thermal rearrangement to produce products (e.g., 2 and 8) with inverted orientations of the cyclopropane rings.The process is shown to involve an intramolecular ene reaction with a bicyclic enol intermediate 13 which was trapped as an E-silyl ether 17.In the presence of D2O, deuterium is incorporated quantitatively into the C-12 methyl groups of 1 and 2.A high kinetic isotope effect is observed for the rearrangement of 1 and its deuterated analogue 24, and the reaction parameters are comparable to those reported for the thermal ring-opening reactions of cis-alkylvinylcyclopropanes and cis-alkyl cyclopropyl ketones.In the presence of weak acid or base, an equilibrium is established between 1, 2, and the hydroazulenic dialdehydes 14 and 15.Dialdehyde 7 reacts less cleanly and incorporates deuterium not only at C-13 but also at C-1 (26).The latter process presumably involves enolization via a sigmatropic hydrogen shift.

The Mechanism of the Thermal Rearrangement of the Marasmane Sesquiterpene (+)-Isovelleral. Cyclopropane Ring Closure via an Intramolecular Ene Reaction

The reversible thermal conversion of the fungal sesquiterpene isovelleral (2) into (1) is a unique intramolecular ene reaction proceeding via the bicyclic enol (3), which is demonstrated by kinetic studies, deuterium incorporation, and the trapping of (3).

VELUTINAL ESTERS OF LACTARIUS VELLEREUS AND L. NECATOR. THE PREPARATION OF FREE VELUTINAL.

Esters of the pentacyclic sesquiterpene velutinal have been isolated from Lactarius species, and converted to the free alcohol by base-catalyzed transesterification in EtOH/EtO(1-).