Five-membered carbocycle construction in the synthesis of <i>Daphniphyllum</i> alkaloids: recent strategic and methodological advances

Zhang, Xiaofeng; Xu, Jing

doi:10.1039/d2qo01410f

Cited by 8 publications

(4 citation statements)

References 105 publications

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“…The Daphniphyllum alkaloids [1a–j] constitute an extraordinarily unique and structurally sophisticated class of natural products. Taming structural diversity, daphniphyllum alkaloids are often classified according to signature structural motifs and the proposed biosynthesis.…”

Section: Introductionmentioning

confidence: 99%

Daphnicyclidin Alkaloids 2001–2023

Gierok,

Hiersemann

2024

Eur J Org Chem

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The Daphniphyllum alkaloids represent a particularly diverse class of complex diterpene alkaloids, which are characterized by their enormous structural diversity. The daphnicyclidins, a subgroup of these alkaloids, stand out due to their unique pentafulvene structural motif. This review article gives an overview of the compounds that have been isolated so far and can be assigned to this subgroup. Furthermore, all synthesis approaches and total syntheses published to date are presented.

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Section: Introductionmentioning

confidence: 99%

Daphnicyclidin Alkaloids 2001–2023

Gierok,

Hiersemann

2024

Eur J Org Chem

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“…Ketene dithioacetals are important building blocks in organic synthesis for the construction of carbo- and heterocyclic compounds . Owing to the push–pull effect of the alkylthio group and carbonyl group, α-oxo ketene dithioacetals are regarded as polarized internal olefins, and the α-C that is adjacent to the carbonyl group is electrophilic.…”

Section: Introductionmentioning

confidence: 99%

Visible-Light-Promoted Regioselective Hydroborylation of Ketene Dithioacetals with NHC-Boranes

An,

Li,

Xia

et al. 2023

J. Org. Chem.

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NHC-boranes have been treated as a reliable source of boryl radicals. In this study, regioselective hydroborylation of ketene dithioacetals with NHC-borane was achieved under mild conditions via a visible-lightpromoted radical chain process using thiophenol as a proton donor and hydrogen atom transfer. This protocol features a low-cost catalyst, good functional group tolerance, a relatively broad range of substrate scope, and good to excellent yields. Moreover, mechanism of this hydroborylation reaction was preliminarily studied.

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“…Selected molecules containing exocyclic olefinic cyclopentene units are shown in Scheme a. However, the synthesis of exocyclic olefinic cyclopentenes is tedious, usually resorting to multistep processes. ,,,,, As shown above, Lu’s [3+2] annulation of allenaotes with electron-deficient alkenes provides an effective and robust means for generating cyclopentenes, which has been applied in the construction of various cyclopentene-containing molecules, including complex natural products . However, the evolution of Lu’s [3+2] annulation for the synthesis of exocyclic olefinic cyclopentenes remains elusive .…”

mentioning

confidence: 99%

Phosphine-Catalyzed [3+2] Annulation of Hepta-2,3,5-trienedioates with Alkenes for the Construction of Exocyclic Olefinic Cyclopentenes

Li,

Zhang,

Han

et al. 2023

J. Org. Chem.

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Hepta-2,3,5-trienedioates 1 have been employed as substrates to explore Lewis base-catalyzed annulation reactions. This leads to the discovery of a phosphine-catalyzed [3+2] annulation of 1 with electron-deficient alkenes for the construction of exocyclic olefinic cyclopentenes in good yields and moderate E:Z ratios under mild conditions. The annulation is believed to proceed in a tandem [3+2] cyclization and double bond migration in which the ε-ester is crucial to both processes. This reaction also showcases a substrate-controlled divergent reactivity compared to that of a previous report.

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Five-membered carbocycle construction in the synthesis of Daphniphyllum alkaloids: recent strategic and methodological advances

Abstract: As the key structural unit, five-membered carbocycles are widely found in the framework of natural products. Among these molecules, Daphniphyllum alkaloids are particularly intriguing targets for synthetic chemists owing to...

Cited by 8 publications

References 105 publications

Daphnicyclidin Alkaloids 2001–2023

Daphnicyclidin Alkaloids 2001–2023

Visible-Light-Promoted Regioselective Hydroborylation of Ketene Dithioacetals with NHC-Boranes

Phosphine-Catalyzed [3+2] Annulation of Hepta-2,3,5-trienedioates with Alkenes for the Construction of Exocyclic Olefinic Cyclopentenes

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