Total synthesis of dl-cyclosativene by cationic olefinic and acetylenic cyclizations

Baldwin, S. W.; Tomesch, John C.

doi:10.1021/jo01296a022

Cited by 13 publications

(4 citation statements)

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“…54 Vinigrol’s susceptibility to acid obviously precluded this harsh approach. A reductive approach using sodium naphthalene 55 as a reducing agent only resulted in unreacted starting material ( 150 ). It is also known that trifluoroethyl ethers can be converted to acetylenic esters using alkyllithium reagents, 56 via a difluorovinyllithium intermediate.…”

Section: Resultsmentioning

confidence: 99%

Evolution of an oxidative dearomatization enabled total synthesis of vinigrol

et al. 2014

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The evolution of the synthetic strategy resulting in a total synthesis of vinigrol is presented. Oxidative dearomatization/intramolecular Diels-Alder cycloaddition has served as the successful cornerstone for all of the approaches. Extensive radical cyclization efforts to form the tetracyclic core resulted in interesting and surprising reaction outcomes, none of which could be advanced to vinigrol. These cyclization obstacles were successfully overcome by using Heck instead of radical cyclizations. The total synthesis features a trifluoroethyl ether protecting group being used for the first time in organic synthesis. The logic of its selection and the group’s importance beyond protecting the C8a hydroxyl group is presented along with a discussion of strategies for its removal. Because of the compact tetracyclic cage the route is built around many unusual reaction observations and solutions have emerged. For example, a first of its kind Grob fragmentation reaction featuring a trifluoroethyl leaving group has been uncovered, interesting interrupted selenium dioxide allylic oxidations have been observed as well as intriguing catalyst and counterion dependent directed hydrogenations.

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Section: Resultsmentioning

confidence: 99%

Evolution of an oxidative dearomatization enabled total synthesis of vinigrol

et al. 2014

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“…Hz) and a second quartet with the same coupling constant which integrated for 1 P at 6, -1.47. Treatment with sodiumliquid ammonia deblocked both the benzyl and allyl 40 protecting groups in one step. Ion-exchange chromatography on Q Sepharose Fast Flow using a gradient of triethylammo-…”

Section: Structure Of Ins(145)p3 and 2-position-modified Analoguesmentioning

confidence: 99%

Synthesis of L-scyllo-inositol 1,2,4-trisphosphate, scyllo-inositol 1,2,4,5-tetrakisphosphate and phosphorothioate and DL-2-deoxy-2-fluoro-myo-inositol 1,4,5-trisphosphate: optical resolution of DL-1-O-allyl-3,6-di-O-benzyl-4,5-O-isopropylidene-scyllo-inositol

Lampe¹,

Liu²,

Mahon³

et al. 1996

J. Chem. Soc., Perkin Trans. 1

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“…A handful of molecules in this family contain a fourth ring leading to compact and complex skeletons comprising of several quaternary carbon atoms. These include longicyclene, 8, 12,13 and it's analogues 9, 14 and 10; 12,13 cyclosativene, 11, [15][16][17][18][19][20][21] cyclocopacamphene, 12, 19,22 and dendronobilin N, 13. 23 Traditionally, tricyclane sesquiterpenoids' main use has been in the perfumery and flavouring industries, although many plant extracts that do contain them have also been used in traditional medicine.…”

Section: Introductionmentioning

confidence: 99%