Gold‐Catalyzed Tandem Cycloisomerization/Cope Rearrangement: An Efficient Access to the Hydroazulenic Motif

Cao, Ziping; Gagosz, Fabien

doi:10.1002/anie.201304497

Cited by 60 publications

(16 citation statements)

References 47 publications

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“…Trienyne 382 cyclizes following a 5- endo -dig pathway through cyclopropyl gold(I) carbene 383 , which gives 384 by 1,2-acyloxy migration followed by a Cope rearrangement to afford hydrozulenic derivative 385 (Scheme 121 ). 325 …”

Section: Gold(i)-catalyzed Reactions Of Propargylic Carboxylatesmentioning

confidence: 99%

Gold(I)-Catalyzed Activation of Alkynes for the Construction of Molecular Complexity

2015

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Section: Gold(i)-catalyzed Reactions Of Propargylic Carboxylatesmentioning

confidence: 99%

Gold(I)-Catalyzed Activation of Alkynes for the Construction of Molecular Complexity

2015

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“…Accordingly, these substrates undergoes an efficient and highly selective reorganization reaction by avoiding competitive 1,3-ester shift or Nazarov-type cyclization. [137] However, Nazarov cyclization is possible in enynyl acetates via tandem Au(I)-catalyzed [3,3]-rearrangement trigger (via 1,3acetyl shift) to lend 2-substituted cyclopentenones. [138] Fensterbank's team in one of their recent works have shown that the 5,7,3-tricyclic skeleton of neomerane sesquiterpenes 41 can be easily synthesized from enynyl propargylic esters 42 featuring Au(I)-catalyzed selective 1,2-acyloxy migration/intramolecular cyclopropanation sequence.…”

Section: 2-selective Ester Shift Reactionsmentioning

confidence: 99%

“…It was shown by the Gagosz's group that hydroazulenic frameworks 39 can be synthesized via Au(I)‐catalyzed cascade 1,2‐ester shift/cycloisomerization/Cope rearrangement of linear trienynes 40 (Scheme 11, eq 1). Accordingly, these substrates undergoes an efficient and highly selective reorganization reaction by avoiding competitive 1,3‐ester shift or Nazarov‐type cyclization [137] . However, Nazarov cyclization is possible in enynyl acetates via tandem Au(I)‐catalyzed [3,3]‐rearrangement trigger ( via 1,3‐acetyl shift) to lend 2‐substituted cyclopentenones [138] .…”

Section: Propargyl Ester Rearrangementsmentioning

confidence: 99%

Regio‐ and Site‐selective Molecular Rearrangements by Homogeneous Gold Catalysis

Praveen

2020

Asian J Org Chem

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Homogeneous gold catalysis for connection and disconnection of carbon-carbon (CÀ C) as well as carbonheteroatom (CÀ X) bond constitutes an important zone in molecular chemistry, since all new or existing organic synthesis relies on the transformation of these chemical bonds. Among the diaspora of molecular transformations, rearrangement and shift reactions occupy a special place in organic chemistry, as they enable the synthesis of molecules of increased complexity from simple precursors. However, the rearrangement in substrates possessing more than one potential reaction site produce more than one isomer and could result in regioselective issues. This challenge of selective synthesis of one regisomer over the other was fairly addressed by gold catalysis on various occasions. To this end, the prowess of homogeneous gold catalysis towards regioselective molecular rearrangement reactions and the contributing parameters are comprehensively reviewed. Also, synthetic applicability of regioselective rearrangements by gold catalysis in total and formal synthesis of several natural products was emphasized.This review also covers the emergence of gold catalyzed migratory/shift selective reactions and could be beneficial for synthetic and medicinal chemists.

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“…Gagosz proposed a similar 1,2-OAc shift followed by the cyclopropanation/Cope rearrangement to afford the desired fused cycloheptadiene derivatives (Scheme 3.14d). 52 Yu has shown that it is possible to use dienediynes 3.15a in these types of cyclization reactions. He proposed that the mechanism goes through the cyclopropanation/…”

Section: Scheme 312 Au-catalyzed Formal (4+3)-cycloadditions Of Diazmentioning

confidence: 99%

Recent Advances in Transition-Metal-Catalyzed (4+3)-Cycloadditions

Lam

Lautens²

2020

Synthesis

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A (4+3)-cycloaddition combines a four-atom synthon and three-atom synthon to form seven-membered rings. In the past decade, many improvements have been made to this class of cycloaddition, including excellent diastereo- and enantioselectivities, both intra- and intermolecularly. Through the strategic use of transition-metal catalysts, acids, bases, and organocatalysts, it is possible to perform the cycloaddition on a variety of substrates, generating novel seven-membered rings. With these advances, (4+3)-cycloaddition has also been applied to the synthesis of biologically relevant compounds and natural products. We exclude the cycloadditions of cyclic dienes such as furan, pyrrole, cyclohexadiene or cyclopentadiene as Chiu, Harmata, Mascareñas and others have recently published thorough reviews on that topic. We will however discuss the recent additions (2009–2020) to the literature for the (4+3)-cycloadditions involving other types of four-atom synthons.1 Introduction2 Rhodium2.1 Cyclopropanation/Cope Rearrangement2.2 C–H activation3 Gold, Silver4 Copper5 Palladium, Platinum, Iridium6 Dual-Activation7 Conclusion

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Gold‐Catalyzed Tandem Cycloisomerization/Cope Rearrangement: An Efficient Access to the Hydroazulenic Motif

Abstract: International audienc

Cited by 60 publications

References 47 publications

Gold(I)-Catalyzed Activation of Alkynes for the Construction of Molecular Complexity

Gold(I)-Catalyzed Activation of Alkynes for the Construction of Molecular Complexity

Regio‐ and Site‐selective Molecular Rearrangements by Homogeneous Gold Catalysis

Recent Advances in Transition-Metal-Catalyzed (4+3)-Cycloadditions

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