Preparation and thermal rearrangement of 2-(tert-butyldimethylsiloxy)-5-methyl-6-exo-[(Z)-3-methyl-1-butenyl]- 4 - exo - vinylbicyclo[3.1.0]hex-2-ene. A total synthesis of (±)-sinularene

Piers, Edward; Jung, Grace

doi:10.1139/v87-279

Cited by 11 publications

(2 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Since its isolation and determination of its AC through an X-ray study, many racemic syntheses of sinularene 218 − were reported to date, however without enantioselective synthesis of this compound. The same finding holds for lemnalol 206 and β-copaene 211 , which were the subject of only racemic syntheses. − The biogenetic relationship between the marine sesquiterpenes neopupukeananes and trachyopsanes was ascertained by a biomimetic rearrangement employed as the key step for the enantioselective first total syntheses of the marine sesquiterpenes (−)-2-(formylamino)-trachyopsane 221 and (+)- ent -2-(isocyano)trachyopsane 223 (Scheme ).…”

Section: Synthesismentioning

confidence: 99%

Tricyclic Sesquiterpenes from Marine Origin

et al. 2017

View full text Add to dashboard Cite

The structure elucidation, biosynthesis, and biological activity of marine carbotricyclic sesquiterpene compounds are reviewed from the pioneering results to the end of 2015. Their total syntheses with a particular emphasis on the first syntheses, enantiomeric versions, and syntheses that led to the revision of structures or stereochemistries are summarized. Overall, 284 tricyclic compounds are classified into fused, bridged, and miscellaneous structures based on 54 different skeletal types. Tricyclic sesquiterpenes constitute an important group of natural products. Their structural diversity and biological activities have generated further interest in the field of drug discovery research, although the exact mechanisms of action of these species are not well known. Furthermore, these tricyclic structures, according to their chemical complexity, are a source of inspiration for chemists in the field of total synthesis for the development of innovative methodologies.

show abstract

Section: Synthesismentioning

confidence: 99%

Tricyclic Sesquiterpenes from Marine Origin

et al. 2017

View full text Add to dashboard Cite

show abstract

“…Piers and co-workers were the first to examine the DVCPR as a key step in the formal synthesis of (±)-quadrone ( 55 , see Scheme 9 ) [ 49 ], and the total syntheses of sinularene ( 59 ) [ 50 ], prezizanol ( 63 ) and prezizaene ( 64 ) [ 51 ]. The synthesis of the cytotoxic sesquiterpenoid quadrone ( 55 ) from Aspergillus terreus [ 52 – 53 ] started from tricyclic ketone 52 [ 54 ], which was converted into tricycle 53 in 12 steps.…”

Section: Reviewmentioning

confidence: 99%

Recent applications of the divinylcyclopropane–cycloheptadiene rearrangement in organic synthesis

Krüger¹,

Gaich²

2014

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

show abstract

Divinylcyclopropane‐CycloheptadieneRearrangement

et al. 1992

View full text Add to dashboard Cite

The first documented report of a possible Cope rearrangement was probably that of Baeyer, who prepared eucarvone by hydrobromination of carvone in 1894. Although the transformation was briefly studied at that time, it was not until the 1950s that this and other Cope‐type rearrangements received detailed attention. The thermal isomerization of cis ‐divinylcyclopropane to cycloheptan‐1,4‐diene was reported by Vogel in 1960 during his studies of the Cope rearrangement of 1,5‐hexadienes annulated by a homologous series of carbocyclic rings. Scores of mechanistic studies followed this discovery upon the realization that the rearrangement could be related to the conceptually similar vinylcyclopropane–cyclopentene isomerization discovered a year earlier. It was also recognized that this rearrangement might be operating in the formation of cycloheptatriene from norcaradiene during photolysis of diazomethane in benzene. The topic received considerable attention in the 1960s, an era of mechanistic investigations of various concerted transformations. During the 1970s it enjoyed exploitation in many synthetic strategies, and the following decade the elements of this rearrangement were incorporated into tandem or multistep procedures in a preconceived manner. Many aspects of the various permutations of the Cope rearrangement have been previously reviewed. The purpose of this review is to summarize the mechanistic, stereochemical, and practical results in this area in the context of the evolution of synthetic achievements during the last 40 years. Also described in this chapter are the transformations of several of the simple heteroatom permutations of this rearrangement in order to render appropriate comparisons of various systems. A discussion addresses those rearrangements of cyclopropanes, oxiranes, thiiranes, and aziridine rings substituted with vicinal vinyl groups. Excluded from this review are rearrangements of those divinylsubstituted three‐membered rings that contain more than a single heteroatom within the reacting manifold. Brief mention of these systems along with a guide to the literature is found in the last section of this chapter. The literature is covered through December 1990. Many of the principal researchers in this field have been contacted and many unpublished transformations have been included in the tables.

show abstract

Preparation and thermal rearrangement of 2-(tert-butyldimethylsiloxy)-5-methyl-6-exo-[(Z)-3-methyl-1-butenyl]- 4 - exo - vinylbicyclo[3.1.0]hex-2-ene. A total synthesis of (±)-sinularene

Cited by 11 publications

References 14 publications

Tricyclic Sesquiterpenes from Marine Origin

Tricyclic Sesquiterpenes from Marine Origin

Recent applications of the divinylcyclopropane–cycloheptadiene rearrangement in organic synthesis

Divinylcyclopropane‐CycloheptadieneRearrangement

Contact Info

Product

Resources

About