The Total Synthesis of (±)‐Naupliolide: A Tetracyclic Sesquiterpene Lactone

Abstract

The first total synthesis of (AE)-naupliolide has been achieved. The synthetic method includes aS immons-Smith cyclopropanation of an allyl alcohol, diastereoselective cleavage of ab enzylidene acetal group,r adical cyclization of an aldehyde with ac yclopropane ring,a nd construction of an eight-membered ring by ring-closing metathesis.Supportinginformation for this article can be found under http://dx.

Selective Synthesis of Cyclooctanoids by Radical Cyclization of Seven‐Membered Lactones: Neutron Diffraction Study of the Stereoselective Deuteration of a Chiral Organosamarium Intermediate

“…[2,3] Ther ace towards the total synthesis of paclitaxel (Taxol) [4] spurred particular interest in the motif and the construction of cyclooctanes has become afertile field (Scheme 1). [5][6][7][8][9][10][11] Among these methods,r adical cyclization approaches are scarce and have relied mainly on radicals generated from halides, [12] ketones [13,14] and aldehydes [15] and 8-endo cyclization modes (Scheme 2A). [16] Samarium diiodide (Kagansr eagent, SmI 2 ) [17,18] is perhaps the most versatile reductive electron transfer (ET) reagent and has been used extensively for carbon-carbon bond forming reactions.…”

Total Syntheses of (+)‐Aquatolide and Related Humulanolides

“…[9] Five groups have published total syntheses of 5. [16] With regard to asteriscunolides,t otal syntheses of 3 and 4 were achieved by the groups of Fernandes [17] and Tr ost, [18] respectively.E ventually,t he group of Li reported an elegant collective synthesis of the compounds 1-6. [16] With regard to asteriscunolides,t otal syntheses of 3 and 4 were achieved by the groups of Fernandes [17] and Tr ost, [18] respectively.E ventually,t he group of Li reported an elegant collective synthesis of the compounds 1-6.…”

Total Syntheses of (+)‐Aquatolide and Related Humulanolides

“…[10][11][12][13][14] Thes tructurally related naupliolide [15] was also synthesized by Ito and co-workers. [16] With regard to asteriscunolides,t otal syntheses of 3 and 4 were achieved by the groups of Fernandes [17] and Tr ost, [18] respectively.E ventually,t he group of Li reported an elegant collective synthesis of the compounds 1-6. [19] Thet otal synthesis of the challenging revised structure of 7b has been completed by two groups.H iemstra and co-workers accomplished the first total synthesis of racemic (AE)-7b through intramolecular [2+ +2] photocycloaddition of an allenic pentenolide in 16 steps (longest linear chain) with 2.2 %o verall yield.…”