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Total synthesis
About: Total synthesis is a research topic. Over the lifetime, 25578 publications have been published within this topic receiving 489319 citations.
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TL;DR: The asymmetric total synthesis of both enantiomers of the potent antitumor antibiotic fredericamycin A is detailed based on the protocol for the construction of its peri-hydroxy polyaromatic skeleton bearing the chirality at the spiro carbon via a strong base-induced cycloaddition of suitably substituted homophthalic anhydrides with an optically active CDEF-ring unit.
Abstract: The asymmetric total synthesis of both enantiomers of the potent antitumor antibiotic fredericamycin A (1) is detailed based on the protocol for the construction of its peri-hydroxy polyaromatic skeleton bearing the chirality at the spiro carbon via a strong base-induced cycloaddition of suitably substituted homophthalic anhydrides (AB-ring unit) with an optically active CDEF-ring unit. Particular attention has been given to the novel synthesis of the optically active spiro carbon center by a stereospecific rearrangement of optically active benzofuzed-trans-epoxy acylates leading to spirocyclopentane-1,1‘-indane systems. This method is quite useful for the construction of an optically active spiro compound and was applied to the synthesis of the optically pure CDEF-ring unit of 1. Cycloaddition of the optically pure CDEF-ring unit to AB-ring units prepared via benzyne afforded two natural and unnatural-type hexacyclic compounds, which were converted to natural and unnatural enantiomers of synthetic 1, and...
116 citations
TL;DR: A convergent, highly stereoselective total synthesis of (-)-spinosyn A is described, involving a sequence involving the highly beta-selective glycosidation reaction of 13 and glycosyl imidate 30.
Abstract: A convergent, highly stereoselective total synthesis of (–)-spinosyn A (1) is described. Key features of the synthesis include the transannular Diels–Alder reaction of macrocyclic pentaene 11 and the transannular Morita–Baylis–Hillman cyclization of 12 that generates tetracycle 26. The total synthesis of (–)-spinosyn A was completed by a sequence involving the highly β-selective glycosidation reaction of 13 and glycosyl imidate 30.
116 citations
TL;DR: The total synthesis and absolute stereochemistry reassignment of (+)-aquaticol has been achieved using the methodology and the total yield of bicyclo-octenone structures utilizing a copper-mediated asymmetric oxidative dearomatization/[4 + 2] dimerization cascade is described.
Abstract: An enantioselective approach to bicyclo[2.2.2]octenone structures utilizing a copper-mediated asymmetric oxidative dearomatization/[4 + 2] dimerization cascade is described. The total synthesis and absolute stereochemistry reassignment of (+)-aquaticol has been achieved using the methodology.
116 citations
TL;DR: This route features a number of key transformations, including an indolyne cyclization to assemble the [4.3.1]-bicyclic scaffold, as well as a late-stage intramolecular nitrene insertion to functionalize the C11 bridgehead carbon en route to the natural product.
Abstract: We report the first total synthesis of (−)-N-methylwelwitindolinone C isothiocyanate. Our route features a number of key transformations, including an indolyne cyclization to assemble the [4.3.1]-bicyclic scaffold, as well as a late-stage intramolecular nitrene insertion to functionalize the C11 bridgehead carbon en route to the natural product.
116 citations
TL;DR: An asymmetric Heck reaction−carbanion capture process was realized for the first time, making possible the catalytic asymmetric synthesis of various functionalized bicyclo[3.3.0]octane derivatives 6 in up to 94% ee as discussed by the authors.
Abstract: An asymmetric Heck reaction−carbanion capture process was realized for the first time, making possible the catalytic asymmetric synthesis of various functionalized bicyclo[3.3.0]octane derivatives 6 in up to 94% ee. Sodium bromide had interesting effects on this asymmetric Heck reaction−carbanion capture process, and these effects were useful for improving the enantiomeric excess. Furthermore, the catalytic asymmetric synthesis of (−)-Δ9(12)-capnellene (7) was achieved for the first time, using 6b as a key intermediate and a radical cyclization as a key step.
116 citations