86996-95-4

Upstream product

• 103412-32-4 1,2-dibenzoyloxyherbertene 
• 369610-42-4 1,1,2-trimethyl-2-(3-hydroxy-2-methoxymethyloxy-5-methylphenyl)cyclopentane 
• 81784-13-6 (1S)-1,2,2-trimethyl-1-(2-methoxy-5-methyl)phenylcyclopentane 
• 304865-24-5 (1R,2R)-2-(2',3'-dimethoxy-5'-methylphenyl)-1,2-dimethylcyclopentyl-1-carbaldehyde 
• 304865-25-6 (1R,2S)-2-(2',3'-dimethoxy-5'-methylphenyl)-1,2-dimethylcyclopentylmethyl alcohol 
• 223751-39-1 (R)-4-(2,3-dimethoxy-5-methylphenyl)-4,5,5-trimethylcyclopent-2-enone 
• 86996-94-3 (-)-herbertenolide 
• 5497-67-6 2,2-dimethyl-4-pentenal 
• 93-51-6 2-Methoxy-4-methylphenol 
• 68278-85-3 3-bromo-4,5-dimethoxy-toluene 
• 6948-30-7 5-bromoveratralaldehyde 
• 16188-57-1 2-iodo-4-methylphenol 
• 369610-30-0 2-iodo-4-methylphenyl 1,2-dimethyl-2-cyclopentenecarboxylate 
• 369610-32-2 epi-herbertenolide 

Downstream Products

• 103412-30-2 (-)-1,2-diacetoxyherbertene 
• 222022-94-8 (1'S)-2-benzyloxy-4-methyl-6-(1',2',2'-trimethylcyclopentyl)phenol 
• 304859-82-3 (1'S)-5-methyl-3-(1',2',2'-trimethylcyclopentyl)-1,2-(diphenylmethylidenedioxy)benzene 
• 124424-22-2 (-)-mastigophorene B 
• 222022-88-0 (1'S)-2-methoxy-5-methyl-3-(1',2',2'-trimethylcyclopentyl)phenol 
• 222022-95-9 (1'S)-3-benzyloxy-4-methoxy-5-(1',2',2'-trimethylcyclopentyl)toluene 
• 304859-88-9 (1'S)-1-bromo-6-methyl-4-(1',2',2'-trimethylcyclopentyl)-2,3-(diphenylmethylidenedioxy)benzene 
• 304859-83-4 (1'S)-2-bromo-5-(1',2',2'-trimethylcyclopentyl)-3,4-(diphenylmethylidenedioxy)benzoic acid 
• 304859-79-8 (1''S,1'''S)-[2'-methoxy-5'-methyl-3'-(1''',2''',2'''-trimethylcyclopentyl)-phenyl] 2-bromo-3,4-dimethoxy-5-(1'',2'',2''-trimethylcyclopentyl)benzoate 
• 304859-85-6 (1'S,1''S)-4-methoxy-3,8-di(1,2,2,-trimethylcyclopentyl)-1-methyl-9,10(diphenylmethylidenedioxy)-dibenzo[b,d]pyran-6-one 
• 304859-84-5 (1''S,1'''S)-[2'-methoxy-5'-methyl-3'-(1''',2''',2'''-trimethylcyclopentyl)-phenyl] 2-bromo-5-(1'',2'',2''-trimethylcyclopentyl)-3,4-(diphenylmethylidenedioxy)benzoate 
• 405063-84-5 3,3'-Dimethoxy-6,6'-dimethyl-4,4'-bis-((S)-1,2,2-trimethyl-cyclopentyl)-biphenyl-2,2'-diol 

Relevant academic research and scientific papers

Enantioselective palladium catalyzed conjugate additions of ortho-substituted arylboronic acids to β,β-disubstituted cyclic enones: Total synthesis of herbertenediol, enokipodin A and enokipodin B

The palladium-catalyzed conjugate addition (Michael addition) of ortho-substituted arylboronic acids to β,β-disubstituted cyclic enones, in particular 3-methyl cyclopent-2-enone and 3-methyl cyclohex-2-enone, is reported. With an achiral bipyridine-based palladium catalyst, good yields are obtained with a variety of ortho-substituted arylboronic acids. In the asymmetric version, good to very high enantiomeric excesses (up to 99% ee) are obtained, though the yields are moderate. The decreased yields are attributed to significant protodeboronation of the arylboronic acid. The developed methodology allows the efficient enantioselective synthesis of the very crowded, biologically active, sesquiterpenes herbertenediol, enokipodin A, and enokipodin B. This journal is the Partner Organisations 2014.

Total synthesis of (±)-herbertenediol

A formal total synthesis of the sesquiterpene (±)-herbertenediol and its dimers mastigophorenes A-D has been accomplished, starting from vanillin via 2,3-dimethoxy-5-methylbenzaldehyde. A combination of Claisen rearrangement and ring-closing metathesis reactions were employed for the generation of the two vicinal quaternary carbons on a cyclopentane ring.

Concise asymmetric synthesis of (-)-herbertenediol

The rearrangement of the optically active 3-aryl-2-methyl-2,3-epoxy tosylate (>98% ee) afforded the α-keto tosylate with a chiral quaternary carbon center and without loss of chirality. Reductive removal of the tosyloxy group gave the keto compound with a chiral quaternary carbon center, which was converted to (-)-herbertenediol (>98% ee).

The rearrangement of 2,3-epoxysulfonates and its application to natural products syntheses: Formal synthesis of (-)-aphanorphine and total syntheses of (-)-α-herbertenol and (-)-herbertenediol

The Lewis acid treatment of 2,3-epoxysulfonates with 2,3-dialkyl substituents or 2-alkyl-3-aryl substituents produced the rearrangement products via C3-cleavage of the oxirane ring in high yields. On the other hand, 2-aryl-3-alkyl-2,3-epoxysulfonates produced the products via C2-cleavage of the oxirane ring. The sulfonyloxy groups of the α-sulfonyloxy ketones, having a chiral benzylic quaternary carbon center obtained by the rearrangement of 2-alkyl-3-aryl-2,3-epoxysulfonates, were reductively eliminated to give the ketones with a chiral benzylic quaternary carbon center. The method was applied to the formal synthesis of (-)-aphanorphine and total syntheses of (-)-α-herbertenol and (-)-herbertenediol.

Total syntheses of neuroprotective mastigophorenes A and B

(-)-Herbertenediol (3) which is regarded as a biosynthetic precursor of mastigophorenes A and B has been effectively synthesized from (R)-1,2-dimethyl-2-cyclopentene carboxylic acid by applying an intramolecular Heck reaction to the construction of the quaternary carbon center, and then horseradish peroxidase-catalyzed oxidative coupling of 3 has given rise to (-)-mastigophorenes A and B. Mastigophorenes A and B have been found to exhibit significant neuroprotective activity in primary cultures of fetal rat cortical neurons.

New route to herbertanes via a Suzuki cross-coupling reaction: Synthesis of herbertenediol

The synthesis of herbertenediol, a relevant member of the herbertane-type sesquiterpene family, is described. The synthesis is based on a new general approach to this group of sesquiterpenes where the herbertane skeleton is constructed using a Suzuki cross-coupling reaction and a [2,3]-sigmatropic Still-Wittig rearrangement as key synthetic steps.

Nondynamic and dynamic kinetic resolution of lactones with stereogenic centers and axes: Stereoselective total synthesis of herbertenediol and mastigophorenes A and B

The stereoselective total synthesis of the sesquiterpene herbertenediol (3) and of its naturally occurring dimers, mastigophorenes A [(P)-1] and B [(M)-1], is described. Following the 'lactone concept', the configuration at the biaryl axis was atropo-dive

New total synthesis of (±)-herbertene, (±)-β-herbertenol and (±)-herbertenediol

The total syntheses of the herbertane sesquiterpenes (±)-herbertene (1), (±)-β-herbertenol (2) and (±)-herbertenediol (5) have been successfully accomplished involving copper-catalysed conjugate addition of Grignard reagents to unsaturated compounds and α

First synthesis of mastigophorenes A and B, by biomimetic oxidative coupling of herbertenediol

The first synthesis of mastigophorenes A and B by oxidative phenolic coupling of partially protected derivatives of their joint natural monomeric half, herbertenediol, is described. The synthesis starts from this diol itself or from the corresponding aldehyde, both available by isolation from the liverwort, Herbertus aduncus. After transformation of herbertenediol to a chemically appropriate monophenolic coupling precursor, the oxidative dehydrodimerization was brought about using (tert-BuO)2, followed by deprotection to give mastigophorenes A and B in their 'natural' atropisomeric ratio, as isolated from the liverwort.

Total syntheses of (-)-herbertenediol, (-)-mastigophorene A, and (-)- mastigophorene B. Combined utility of chiral bicyclic lactams and chiral aryl oxazolines

A nonracemic bicyclic lactam has been used to construct a chiral cyclopentane containing vicinal quaternary carbon centers in optically pure form, which is common to all of the title compounds. An oxazoline-mediated asymmetric Ullmann coupling was then utilized to establish chirality about the biaryl axis of mastigophorenes A and B. Through the course of this synthesis, it was clearly demonstrated that smaller chiral auxiliaries lead to higher levels of atroposelection, a previously unknown phenomenon of the asymmetric Ullmann coupling.