Gold(I)-Catalyzed Polycyclization of Linear Dienediynes to Seven-Membered Ring-Containing Polycycles via Tandem Cyclopropanation/Cope Rearrangement/C–H Activation

Cai, Peijun; Wang, Yi; Liu, Cheng‐Hang; Yu, Zhi‐Xiang

doi:10.1021/ol5028706

Cited by 52 publications

(26 citation statements)

References 53 publications

(18 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In 2014, Yu's group (Cai et al, 2014) reported a cascade cyclization for polycyclic carbocycles via gold(I)-catalyzed sequential cyclopropanation, cope rearrangement, and C-H functionalization of linear dienediyne substrates. A 6/7/5-fused tricyclic skeleton can be obtained, which exists in some natural diterpenes such as daphnane and tigliane families ( Figure 1C).…”

Section: Construction Of Polycyclic Carbocyclesmentioning

confidence: 99%

Recent Advances in Construction of Polycyclic Natural Product Scaffolds via One-Pot Reactions Involving Alkyne Annulation

Zheng

Hua

2020

Front. Chem.

View full text Add to dashboard Cite

Polycyclic scaffolds are omnipresent in natural products and drugs, and the synthetic strategies and methods toward construction of these scaffolds are of particular importance. Compared to simple cyclic ring systems, polycyclic scaffolds have higher structure complexity and diversity, making them suitable for charting broader chemical space, yet bringing challenges for the syntheses. In this review, we surveyed progress in the past decade on synthetic methods for polycyclic natural product scaffolds, in which the key steps are one-pot reactions involving intermolecular or intramolecular alkyne annulation. Synthetic strategies of selected polycyclic carbocycles and heterocycles with at least three fused, bridged, or spiro rings are discussed with emphasis on the synthetic efficiency and product diversity. Recent examples containing newly developed synthetic concepts or toolkits such as collective and divergent total synthesis, gold catalysis, C-H functionalization, and dearomative cyclization are highlighted. Finally, several "privileged synthetic strategies" for "privileged polycyclic scaffolds" are summarized, with discussion of remained challenges and future perspectives.

show abstract

Section: Construction Of Polycyclic Carbocyclesmentioning

confidence: 99%

Recent Advances in Construction of Polycyclic Natural Product Scaffolds via One-Pot Reactions Involving Alkyne Annulation

Zheng

Hua

2020

Front. Chem.

View full text Add to dashboard Cite

show abstract

“…Yu and coworkers designed a new gold-catalyzed reaction for the synthesis of 5,7,6-tricyclic ring systems by the polycyclization of linear dienediynes 154 with high diastereocontrol in one step (Scheme 37). [36] There is another chance of creating a different tricyclic compound by the deprotonation followed by prodeauration of carbocation intermediate and regenerate the gold catalyst. They have applied this strategy to a wide variety of substrates in the presence of 10 mol% of gold catalyst 155 in DCE at room temperature affording good to excellent yields of the products.…”

Section: Gold-catalyzed Coupling Reactions Through Csp 2 à H Bond Actmentioning

confidence: 99%

“…Proposed reaction mechanism for the gold-catalyzed synthesis of seven membered ring containing polycycles via tandem polycyclization. Adapted from ref 36. with permission.…”

mentioning

confidence: 99%

Advances and Prospects in Gold‐Catalyzed C−H Activation

et al. 2020

View full text Add to dashboard Cite

The omnipresent character of C−H bonds in organic molecules gives a wide variety of opportunities for the synthesis of a number of functionalized molecules by the activation of the C−H bonds. One of those methods is gold‐catalyzed C−H activation. Recent developments in the area of gold‐catalyzed C−H activation involves annulation reactions leading to the formation of heterocyclic compounds, Au‐catalyzed cross coupling reactions, and C−H functionalization reactions with high atom efficiency. In this short review we summarize the developments and studies carried out in gold‐catalyzed C−H activation over the past decade.

show abstract

“…The reaction sequence on 73 followed a Cope rearrangement, formation of a strained seven‐membered‐cyclic allene ( 74 ), and an aliphatic C−H activation triggering 1,2‐H (or OAc) shifts. The long cascade reaction sequence efficiently built up fused 5,7,6‐tricyclic ring systems ( 77 ) in one step and with a high diastereoselectivity …”

Section: Synthesis Of Bio‐relevant Small To Medium Ring‐heterocyclesmentioning

confidence: 99%

Gold(I) Catalyzed Enyne Cycloisomerization – A Roadmap to Privileged Heterocyclic Scaffolds

Lee

Kumar

2018

Israel Journal of Chemistry

View full text Add to dashboard Cite

Gold(I) catalyzed cycloisomerization reaction is one of the key transformations that remain underexplored to build molecular diversity and complexity. In this review, we summarize synthesis endeavors where enyne cycloisomerization chemistry was utilized to form structurally intriguing as well as biologically relevant heterocyclic scaffolds. To this goal, most of the efforts tend to exploit gold carbene type intermediates, often supporting a cyclopropane ring and transform them into new scaffolds. Various examples have been grouped together to highlight the role of presence or absence of external heteroatom nucleophiles in modulating reactive intermediates into novel molecular frameworks. The last section is devoted to the emerging role of gold(I) catalyzed cycloisomerization reactions in driving the divergent synthesis approaches wherein a common substrate can be transformed into distinct molecular scaffolds by merely varying reaction conditions or gold complexes.

show abstract

Gold(I)-Catalyzed Polycyclization of Linear Dienediynes to Seven-Membered Ring-Containing Polycycles via Tandem Cyclopropanation/Cope Rearrangement/C–H Activation

Abstract: The presented step‐economic synthesis of complex molecules proceeds with moderate to excellent diastereoselectivity.

Cited by 52 publications

References 53 publications

Recent Advances in Construction of Polycyclic Natural Product Scaffolds via One-Pot Reactions Involving Alkyne Annulation

Recent Advances in Construction of Polycyclic Natural Product Scaffolds via One-Pot Reactions Involving Alkyne Annulation

Advances and Prospects in Gold‐Catalyzed C−H Activation

Gold(I) Catalyzed Enyne Cycloisomerization – A Roadmap to Privileged Heterocyclic Scaffolds

Contact Info

Product

Resources

About