Total synthesis of the sesquiterpenes (+)-daucene, (+)-carotol, and (–)-daucol

Broissia, H. De; Levisalles, J.; Rudler, H.

doi:10.1039/c39720000855

Cited by 20 publications

(12 citation statements)

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“…Daucene ( 233 ) is a member of the carotane-type sesquiterpenes and has an unusual hydroazulene skeleton. The daucane (carotane) sesquiterpenes all share a bicyclo[5.3.0]decane core with diverse functionality and varied degrees of oxidation (Figure ) and have been shown to exhibit diverse biological activities. − During the years, several total syntheses of daucene ( 233 ) have been reported. − Seto and co-workers employed a highly regioselective intramolecular [2 + 2] photocycloaddition followed by a retro-aldol reaction to access a variety of carotane-type terpenes, including (±)-daucene . Irradiation of enone 239 resulted in efficient and regioselective photocyclization to afford photoproduct 240 in 88% yield (Scheme ).…”

Section: [2 + 2] Photocycloadditionsmentioning

confidence: 99%

Photochemical Approaches to Complex Chemotypes: Applications in Natural Product Synthesis

2016

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The use of photochemical transformations is a powerful strategy that allows for the formation of a high degree of molecular complexity from relatively simple building blocks in a single step. A central feature of all light-promoted transformations is the involvement of electronically excited states, generated upon absorption of photons. This produces transient reactive intermediates and significantly alters the reactivity of a chemical compound. The input of energy provided by light thus offers a means to produce strained and unique target compounds that cannot be assembled using thermal protocols. This review aims at highlighting photochemical transformations as a tool for rapidly accessing structurally and stereochemically diverse scaffolds. Synthetic designs based on photochemical transformations have the potential to afford complex polycyclic carbon skeletons with impressive efficiency, which are of high value in total synthesis.

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Section: [2 + 2] Photocycloadditionsmentioning

confidence: 99%

Photochemical Approaches to Complex Chemotypes: Applications in Natural Product Synthesis

2016

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“…It was assigned an absolute configuration enantiomeric to that indicated in 7, based on its co-occurrence with ( + )-a-cedrene, ( + )-prezizaene and ( + )-zizaene. We visualized by analogy to the co-formation of daucene (6) and acoradiene 7 from 5. as described above, a stereospecific conversion of carotol (1) of known absolute configuration (14)(15)(16)(17)(18) into acoradiene 7, thus unequivocally establishing the absolute configuration of the new acoradiene.…”

mentioning

confidence: 72%

Chemistry of the Carotane Sesquiterpenes V. Biosimulated Conversions

Zalkow¹,

Clower²,

Gordon³

et al. 1980

J. Nat. Prod.

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“…synthon include the use of carvomenthone in the synthesis of copacamphor and copacamphene, 56 caran-2-one in the synthesis of cubebol and the cubabenes 57 and (-)-carvone in the synthesis of (+)-daucene and (+)-carotol. 58 Carvone has been used as α chiral starting material for the synthesis of eudesmanes and dihydroagarofurans 59 as well as for more complex terpenoids and steroids such as the sesquiterpenoid perihysin E. 60 The cyclisation of carvone epoxide 61 by Ti(III) gave 61 functionalised pinenes such as 62 (Scheme 16). The cleavage of these has afforded routes to chiral cyclohexenones (e.g.…”

Section: Chiral Cyclohexane Synthonsmentioning

confidence: 99%