Asymmetric Synthesis of Nidulalin A and Nidulaxanthone A: Selective Carbonyl Desaturation Using an Oxoammonium Salt DOI Creative Commons
Kaijie Ji, Richard P. Johnson, James McNeely

et al.

Published: Jan. 10, 2024

Nidulaxanthone A is a dimeric, dihydroxanthone natural product which was isolated in 2020 from Aspergillus sp. Structur-ally, the compound features an unprecedented heptacyclic 6/6/6/6/6/6/6 ring system unusual for xanthone dimers. Biosynthetically, nidulaxanthone originates monomer nidulalin via stereoselective Diels-Alder dimeri-zation. To expedite synthesis of and study proposed dimerization, we developed methodology involving use allyl triflate chromone ester activation followed by vinylogous addition to rapidly forge scaffold four-step sequence also ketone desaturation using Bobbitt’s oxoammonium salt. The asymmetric achieved acylative kinetic resolution (AKR) chiral, racemic 2H-nidulalin A. Dimerization en-antioenriched solvent-free, thermolytic conditions. Computational studies have been conducted probe both (4+2) dimerization events.

Language: Английский

Five-membered carbocycle construction in the synthesis of Daphniphyllum alkaloids: recent strategic and methodological advances DOI
Xiaofeng Zhang, Jing Xu

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(23), P. 6708 - 6716

Published: Jan. 1, 2022

In this review article, we summarize novel or non-standard strategies and methods for the five-membered carbocycle construction in recent Daphniphyllum alkaloid synthesis.

Language: Английский

Citations

11
Synthesis of Tetracyclic Core Structure of Daphnezomines A and B DOI Open Access
Jingping Hu, Wenqing Chen, Yuyang Jiang

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 43(1), P. 171 - 171

Published: Jan. 1, 2023

Among the tiniest Daphniphyllum alkaloid subfamilies, daphnezomine A-type alkaloids consist of only three known members, namely A (1), B (2) and dapholdhamine B. These contain a unique aza-adamantane core along with nine contiguous stereogenic centers, thus presenting remarkable synthetic challenges.The synthesis tetracyclic structure 1 2 was reported.The key steps in our approach include Huang's amide-activa tion-annulation Hutchins-Kabalka reductive rearrangement.

Language: Английский

Citations

5
Total synthesis of a putative yuzurimine-type Daphniphyllum alkaloid C14‑epi-deoxycalyciphylline H DOI
Jingping Hu, Jing Xu

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 35(4), P. 108733 - 108733

Published: June 28, 2023

Language: Английский

Citations

4
Asymmetric Synthesis of Nidulalin A and Nidulaxanthone A: Selective Carbonyl Desaturation Using an Oxoammonium Salt DOI Creative Commons
Kaijie Ji, Richard P. Johnson, James McNeely

et al.

Published: Aug. 9, 2023

Nidulaxanthone A is a dimeric, dihydroxanthone natural product which was isolated in 2020 from Aspergillus sp. Structur-ally, the compound features an unprecedented heptacyclic 6/6/6/6/6/6/6 ring system unusual for xanthone dimers. Biosynthetically, nidulaxanthone originates monomer nidulalin via stereoselective Diels-Alder dimeri-zation. To expedite synthesis of and study proposed dimerization, we developed methodology involving use allyl triflate chromone ester activation followed by vinylogous addition to rapidly forge scaffold four-step sequence also ketone desaturation using Bobbitt’s oxoammonium salt. The asymmetric achieved acylative kinetic resolution (AKR) chiral, racemic 2H-nidulalin A. Dimerization en-antioenriched solvent-free, thermolytic conditions. Computational studies have been conducted probe both (4+2) dimerization events.

Language: Английский

Citations

4
Asymmetric Synthesis of Nidulalin A and Nidulaxanthone A: Selective Carbonyl Desaturation Using an Oxoammonium Salt DOI Creative Commons
Kaijie Ji, Richard P. Johnson, James McNeely

et al.

Published: Jan. 10, 2024

Nidulaxanthone A is a dimeric, dihydroxanthone natural product which was isolated in 2020 from Aspergillus sp. Structur-ally, the compound features an unprecedented heptacyclic 6/6/6/6/6/6/6 ring system unusual for xanthone dimers. Biosynthetically, nidulaxanthone originates monomer nidulalin via stereoselective Diels-Alder dimeri-zation. To expedite synthesis of and study proposed dimerization, we developed methodology involving use allyl triflate chromone ester activation followed by vinylogous addition to rapidly forge scaffold four-step sequence also ketone desaturation using Bobbitt’s oxoammonium salt. The asymmetric achieved acylative kinetic resolution (AKR) chiral, racemic 2H-nidulalin A. Dimerization en-antioenriched solvent-free, thermolytic conditions. Computational studies have been conducted probe both (4+2) dimerization events.

Language: Английский

Citations

1