Described herein is a synthetic strategy for the total synthesis of (±)-phomoidride D. This highly efficient and stereoselective approach provides rapid assembly of the carbocyclic core by way of a tandem phenolic oxidation/intramolecular Diels–Alder cycloaddition. A subsequent SmI2-mediated cyclization cascade delivers an isotwistane intermediate poised for a Wharton fragmentation that unveils the requisite bicyclo[4.3.1]decene skeleton and sets the stage for synthesis completion.
Leung, Joyce C.,Bedermann, Aaron A.,Njardarson, Jón T.,Spiegel, David A.,Murphy, Graham K.,Hama, Naoto,Twenter, Barry M.,Dong, Ping,Shirahata, Tatsuya,McDonald, Ivar M.,Inoue, Munenori,Taniguchi, Nobuaki,McMahon, Travis C.,Schneider, Christopher M.,Tao, Nancy,Stoltz, Brian M.,Wood, John L.
An efficient and highly stereoselective approach toward the phomoidride family of natural products is described. The carbocyclic core structure was assembled using a tandem phenolic oxidation/Diels-Alder cycloaddition and a tandem 5-exo-trig/5-exo-trig radical cyclization to deliver an isotwistane intermediate that, upon a late-stage xanthate-initiated Grob fragmentation, furnishes the requisite bicyclo[4.3.1]decene.
Murphy, Graham K.,Shirahata, Tatsuya,Hama, Naoto,Bedermann, Aaron,Dong, Ping,McMahon, Travis C.,Twenter, Barry M.,Spiegel, David A.,McDonald, Ivar M.,Taniguchi, Nobuaki,Inoue, Munenori,Wood, John L.
p. 477 - 489
(2013/03/14)
Cyclic Diynes by Alkyne Metathesis
The preparation of α,ω-diynes with methyl groups at the termini (11a-i) is described. The methylene groups between the alkyne units vary between n = 12 (a) and n = 4 (i). Ring closing metathesis with Mo(CO) 6/CF3C6H4OH yielded the monocyclic alkyne 12a with 11a as starting material, whereas 11b-g yielded the cyclic diynes 13b-g. Detailed structural parameters were obtained for 13b and 13c by X-ray crystallography.
Hellbach, Bjoern,Gleiter, Rolf,Rominger, Frank
p. 2535 - 2541
(2007/10/03)
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