Stereoselective carbon–carbon bond forming reactions of chiral cyclopent-2-enone and cyclopentene-1-methanol, both spiro-connecting a 1,2:5,6-di-O-isopropylidene-α-d-glucofuranosyl ring

ORTHOESTER CLAISEN REARRANGEMENT OF AD-GLUCOSE-DERIVED SPIROCYCLIC SUBSTRATE

“…12 In contrast, the ␤-isomers 6 and 8 were obtained both as the major rearrangement products in the present studies. 12 In contrast, the ␤-isomers 6 and 8 were obtained both as the major rearrangement products in the present studies.…”

“…[1][2][3] As part of continuing interests in the transformation of carbohydrates into a variety of multifunctionalized building blocks, we have studied the orthoester Claisen rearrangements of some carbohydrate-derived allylic alcohols. 12 Spiro compounds are frequently found in nature as core skeletons of a variety of natural terpenoids, represented by spirovetivane (vetispirane), acorane, and chamigranetype sesquiterpenoids (Figure 1). 12 Spiro compounds are frequently found in nature as core skeletons of a variety of natural terpenoids, represented by spirovetivane (vetispirane), acorane, and chamigranetype sesquiterpenoids (Figure 1).…”

Macrolactonizations in the Total Synthesis of Natural Products

“…To date, the Yamaguchi protocol and variations have been used in more than 200 synthetic applications, including eight-membered lactones; , nine-membered halicholactone , and a nine-membered intermediate to laurencin; 10-membered didemninlactone, decarestricine, mueggelone, , hebarumin, and ascidiatrienolide; epothilones A, B, D, E, and F and congeners; ,− macrolactin A; erythronolides and analogues; ,,,,,− oleandolide; ,,, lankanolide; deoxytedanolide; mycinolide; brefeldin; − mycotycin; roxaticin; ,, colletol; , colletallol; clado...…”

“…[223][224][225][226][227] The latter problem is usually solved (Scheme 27) by performing the macrolactonization on the ynoic seco-acid and then reducing the triple bond, as illustrated in the synthesis of laulimalide. 227 To date, the Yamaguchi protocol and variations have been used in more than 200 synthetic applications, including eightmembered lactones; 228,229 nine-membered halicholactone 230,231 and a nine-membered intermediate to laurencin; 232 10-membered didemninlactone, 233 decarestricine, 234 mueggelone, 235,236 hebarumin, 237 and ascidiatrienolide; 238 cyclodepsipeptides such as geodiamolide, 342 globomycin, 343 and stevastelin; 344 nonactin [345][346][347][348] aspicilin; 293,349-352 44-membered swhinholide; 72,[353][354][355] acutiphycin; 356,357 scytophycin; 69,358,359 aplyronine A; 67,360-362 aplyolide; 363,364 hygrolidin; 198 nargenicin and dinemycin A precursors; 365,366 bafilomycin, where the Mukaiyama, Keck, and Palomo protocols failed; 367 apoptolidinone; 61,62,368,369 conglobatin; 209 and macrocyclic glycolipids, 12 such as tric...…”

Update 1 of: Macrolactonizations in the Total Synthesis of Natural Products

“…To date, the Yamaguchi protocol and variations have been used in more than 340 synthetic applications, including eight-membered lactones − such as topsentolide A1 and solandelactone E; − nine-membered halicholactone , and a nine-membered intermediate to laurencin; 10-membered lactones such as didemninlactone, aigialomycin, aspergillides, − aspinolides, , and decarestricine; − exiguolide; , cytotoxic macrolide FD-891; , the bacterial DNA primase inhibitor Sch642305; , iriomoteolide; lituarines B and C; neopeltolide; ,− chloriolide; , oxopolyene macrolide RK-397; , milbemycin; mueggelone; − herbarumin; herbarumin III; , ascidiatrienolide; epothilones A, B, D, E, and F and congeners; ,− lasonolide; macrolactin A; microcarpalide; , erythronolides and analogues; ,,,,,− ,− leiodolide; oleandolide; ,…”