Innovation in protecting-group-free natural product synthesis

Hui, Chunngai; Chen, Fang; Pu, Fan; Xu, Jing

doi:10.1038/s41570-018-0071-1

Cited by 53 publications

(32 citation statements)

References 190 publications

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“…However, the prior protection of the reactive functional groups, such as the hydroxy and amino groups, are still necessary for most of the all-carbon [3 + 2] cycloaddition reactions. We predict that further development of the all-carbon [3 + 2] cyclization with the reactive functional groups’ compatibilities and/or without the use of protecting groups [ 83 – 84 ] can improve the synthetic efficiency and make this class of reactions more attractive to the synthetic scientist for applications. Lastly, we anticipate that the all-carbon [3 + 2] cycloaddition will gain further attention from the synthetic community, including scientists from academia and pharmaceutical industry, for methodic innovation and the efficient synthesis of biologically important natural products.…”

Section: Discussionmentioning

confidence: 99%

All-carbon [3 + 2] cycloaddition in natural product synthesis

Wang¹,

Liu²

2020

Beilstein J. Org. Chem.

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Many natural products possess interesting medicinal properties that arise from their intriguing chemical structures. The highly-substituted carbocycle is one of the most common structural features in many structurally complicated natural products. However, the construction of highly-substituted, stereo-congested, five-membered carbocycles containing all-carbon quaternary center(s) is, at present, a distinct challenge in modern synthetic chemistry, which can be accessed through the all-carbon [3 + 2] cycloaddition. More importantly, the all-carbon [3 + 2] cycloaddition can forge vicinal all-carbon quaternary centers in a single step and has been demonstrated in the synthesis of complex natural products. In this review, we present the development of all-carbon [3 + 2] cycloadditions and illustrate their application in natural product synthesis reported in the last decade covering 2011–2020 (inclusive).

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Section: Discussionmentioning

confidence: 99%

All-carbon [3 + 2] cycloaddition in natural product synthesis

Wang¹,

Liu²

2020

Beilstein J. Org. Chem.

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“…The polymer support might be a linear soluble species, or porous cross-linked polystyrene prepared by copolymerization of styrene with divinylbenzene, having a different density of crosslinks. The chemically bound functional group might be a reagent, a protecting group, a ligand, a metal complex catalyst or some other catalytic species e.g., an acid or base, or a phase transfer catalyst [2].…”

Section: Chloromethylatedmentioning

confidence: 99%

Synthesis and Applications of Polymeric Reagent p-Substituted Triphenylamine

Abu-Abdoun

2021

J. Res. Updates Polym. Sci.

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Chemical modification of chloromethylstyrene - styrene copolymer throughout reaction of p-substituted carboxylic acid group of bis-(4,4`-dibromo)-4``-triphenylamine carboxylic acid with the chloromethyl group attached to a phenyl group was carried out on soluble copolymer and polymeric cross-linked copolymer. Chemical oxidation of the neutral p-substituted triphenylamine with antimony pentachloride in dichloromethane solvent gives the corresponding cation - radical salt with the counter ion antimony hexachloride (SbCl6-). The isolated deep blue color cation radical salt is soluble or in insoluble (resin) form in the copolymer was used as a thermal cationic initiator for the polymerization of epoxy and vinyl monomers at room temperature. The cation radical resin showed good activity and stability compared to the soluble polymeric cation radical, both can initiate the cationic polymerization of cyclohexene oxide and N-vinylcarbazole in dichloromethane at room temperature.

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“…[26] Thep resented syntheses feature ap alladiumcatalyzed oxidative cyclization to assemble the [3.2.1]bicyclic moiety,aClaisen rearrangement/lactone formation sequence to construct the Cring, an intramolecular Wittig reaction to form the Dring, and individual transformations of pallambins Ca nd Dt og enerate pallambins Aa nd B. [26] Thep resented syntheses feature ap alladiumcatalyzed oxidative cyclization to assemble the [3.2.1]bicyclic moiety,aClaisen rearrangement/lactone formation sequence to construct the Cring, an intramolecular Wittig reaction to form the Dring, and individual transformations of pallambins Ca nd Dt og enerate pallambins Aa nd B.…”

Section: Angewandte Chemiementioning

confidence: 99%

“…In summary,w eh ave accomplished the first asymmetric total syntheses of pallambins A-D in 15-16 steps from known cyclohexenone 8 without the use of protecting groups.T he success of this protecting-group-free synthesis was mainly dependent on several highly chemo-and stereoselective reactions. [26] Thep resented syntheses feature ap alladiumcatalyzed oxidative cyclization to assemble the [3.2.1]bicyclic moiety,aClaisen rearrangement/lactone formation sequence to construct the Cring, an intramolecular Wittig reaction to form the Dring, and individual transformations of pallambins Ca nd Dt og enerate pallambins Aa nd B. During the course of this work, am ild method for the dehydrobromination of a-bromoketones was also developed, and the scope of this transformation was investigated.…”

Section: Angewandte Chemiementioning

confidence: 99%

Enantioselective Total Syntheses of Pallambins A–D

et al. 2019

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The first enantioselective total syntheses of (À)pallambins A-D have been achieved in 15 or 16 steps from aknownchiral cyclohexenone.Salient features of the syntheses include ap alladium-catalyzed oxidative cyclization to assemble the [3.2.1]bicyclic moiety,a nE schenmoser-Claisen rearrangement/lactone formation sequence to construct the Cring, an intramolecular Wittig reaction to form the Dring, and individual transformations of pallambins Cand Dtogenerate pallambins Aa nd B. The described synthesis avoids protecting-group manipulations through the design of highly chemoand stereoselective transformations.D uring the course of this work, ap alladium-catalyzed method for the dehydrobromination of a-bromoketones was developed, and the scope of this transformation was also investigated.

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Innovation in protecting-group-free natural product synthesis

Cited by 53 publications

References 190 publications

All-carbon [3 + 2] cycloaddition in natural product synthesis

All-carbon [3 + 2] cycloaddition in natural product synthesis

Synthesis and Applications of Polymeric Reagent p-Substituted Triphenylamine

Enantioselective Total Syntheses of Pallambins A–D

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