Related Experiment Video
Updated: Jun 14, 2025
05:17
Functionalized Spirocyclic Heterocycle Synthesis and Cytotoxicity Assay
Published on: February 9, 2021
1.5K
Concise Synthesis of Cyctetryptomycin A and B Enabled by Zr-Catalyzed Dimerization
Longhui Yu1, Hiroshige Ogawa1, Shangzhao Li1
1The Hong Kong University of Science and Technology (HKUST), Clear Water Bay, Kowloon, Hong Kong SAR, China.
Angewandte Chemie (International Ed. in English)
|August 31, 2024
Summary
Researchers developed a novel Zr-catalyzed method for synthesizing cyctetryptomycin A and B, complex natural products. This breakthrough enables the first total synthesis and provides new insights into their formation mechanisms.
Area of Science:
- Organic Chemistry
- Catalysis
- Natural Product Synthesis
Background:
- Cyctetryptomycin A and B are complex tetrameric natural products.
- Total synthesis of these compounds has not been previously reported.
Purpose of the Study:
- To develop a concise synthetic strategy for cyctetryptomycin A and B.
- To achieve the first total synthesis of cyctetryptomycin A and B.
- To elucidate the mechanism of the Zr-catalyzed radical coupling.
Main Methods:
- Utilized a Zr catalyst for constructing quaternary carbon centers.
- Employed a Zr-catalyzed radical coupling for dimerization.
- Investigated the reaction mechanism using experimental and theoretical methods.
- Extended the synthetic approach to other dimeric natural products.
Main Results:
- Achieved the first total synthesis of cyctetryptomycin A and B.
- Demonstrated a practical approach for creating two consecutive quaternary carbon centers.
- Identified 1,2-bis(diphenylphosphino)ethane (dppe) as an essential additive for the Zr-catalyzed reaction.
- Elucidated the role of dppe in the catalytic cycle.
- Successfully synthesized tetratryptomycin A, dibrevianamide F, and ditryptophenaline.
- Newly elucidated the synthetic mechanism of cyctetryptomycin A and B via oxidative macrocyclization.
Conclusions:
- A novel and efficient Zr-catalyzed synthetic strategy for cyctetryptomycin A and B has been established.
- The study provides significant advancements in the total synthesis of complex natural products.
- Mechanistic insights into the Zr-catalyzed radical dimerization and oxidative macrocyclization were gained.
![Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F60786.jpg&w=3840&q=50)
Related Concept Videos
01:11Aryldiazonium Salts to Azo Dyes: Diazo Coupling
2.9K
The reaction of weakly electrophilic aryldiazonium (also called arenediazonium) salts with highly activated aromatic compounds leads to the formation of products with an —N=N— link, called an azo linkage. This reaction, presented in Figure 1, is known as diazo coupling and occurs without the loss of the nitrogen atoms of the aryldiazonium salt. Highly activated aromatic compounds such as phenols or arylamines favor the diazo coupling reaction. The coupling generally occurs at the...
2.9K
01:17Ziegler–Natta Chain-Growth Polymerization: Overview
3.2K
Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
3.2K
01:20Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
1.9K
Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...
1.9K
01:16Cycloaddition Reactions: Overview
2.5K
Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
2.5K
01:27Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation
2.1K
Robinson annulation is a base-catalyzed reaction for the synthesis of 2-cyclohexenone derivatives from 1,3-dicarbonyl donors (such as cyclic diketones, β-ketoesters, or β-diketones) and α,β-unsaturated carbonyl acceptors. Named after Sir Robert Robinson, who discovered it, this reaction yields a six-membered ring with three new C–C bonds (two σ bonds and one π bond).
2.1K
01:22Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
1.9K
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
1.9K