Gold-Catalyzed Tandem 1,3-Migration/[2 + 2] Cycloaddition of 1,7-Enyne Benzoates to Azabicyclo[4.2.0]oct-5-enes

Rao, Weidong; Susanti, Dewi; Chan, Philip Wai Hong

doi:10.1021/ja2052304

Cited by 113 publications

(51 citation statements)

References 53 publications

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“…The preferred alkene activation versus allenes was recently observed in the cascade 1,3-migration/[2 + 2] cycloaddition of 1,7-enyne benzoates (Scheme 23) [59]. When 83 was heated in presence of the silver free gold complex 20c a variety of highly substituted azabicyclo[4.2.0]oct-5-enes 84 was obtained in good yields as a single regio- and diastereoisomer.…”

Section: Reviewmentioning

confidence: 83%

New developments in gold-catalyzed manipulation of inactivated alkenes

Chiarucci

Bandini

2013

Beilstein J. Org. Chem.

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SummaryOver the recent years, the nucleophilic manipulation of inactivated carbon–carbon double bonds has gained remarkable credit in the chemical community. As a matter of fact, despite lower reactivity with respect to alkynyl and allenyl counterparts, chemical functionalization of isolated alkenes, via carbon- as well as hetero atom-based nucleophiles, would provide direct access to theoretically unlimited added value of molecular motifs. In this context, homogenous [Au(I)] and [Au(III)] catalysis continues to inspire developments within organic synthesis, providing reliable responses to this interrogative, by combining crucial aspects such as chemical selectivity/efficiency with mild reaction parameters. This review intends to summarize the recent progresses in the field, with particular emphasis on mechanistic details.

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Section: Reviewmentioning

confidence: 83%

New developments in gold-catalyzed manipulation of inactivated alkenes

Chiarucci

Bandini

2013

Beilstein J. Org. Chem.

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“…It was proposed that the unfavorable steric interactions avoided the nucleophilic addition of olefin to the activated allene. Instead, addition of enol to the cationic gold activated olefin ( 101 ) in a 6‐ exo‐ trig manner delivered the tetrahydropyridinyl oxenium cation intermediate ( 102 ) that finally formed azabicyclo[4.2.0]oct‐5‐enes ( 103 , Figure a) …”

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

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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.

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“…In 2011 the Chan group discovered a domino aminocyclization/1,3‐sulfonyl migration of N ‐sulfonylaminobutynols 12 , which they further elaborated in 2013 (Scheme ) 38. Au‐assisted cyclization toward 13 is followed by dehydration and 1,3‐sulfonyl migration, or the other way around, affording pyrroles 14 .…”

Section: N‐nucleophilesmentioning

confidence: 99%

Homogeneous Gold‐Catalyzed Cyclization Reactions of Alkynes with N‐ and S‐Nucleophiles

et al. 2015

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This review covers the formation of N-a nd S-containing heterocycles,i nitiated by gold-catalyzed nucleophilic attack of N-o rS-nucleophiles ontoa lkynes. These typeso fn ucleophiles have been somewhat overlooked as compared to their C-o rO-counterparts in other reviews.I nt his particularw ork, their intramolecular gold-mediated attack ontoa lkynesi sr eviewedi nd epth.I ti ss tructured in such af ashion that the reader will get ac learv iew of which substrates react in which cyclization mode. 1I ntroduction 2N-Nucleophiles 2.Scheme1.endo-a nd exo-dig cyclization modes for heteroatom attack onto Au-activated triple bonds. REVIEWSWouter Debrouwer et al. Scheme 2. Au(I)-catalyzed formationo fp yrroles from homopropargylic azidesb yana cetylenic Schmidt reaction. Scheme3.AuCl 3 -catalyzed preparation of fluorinated pyrroles.Scheme4.Pyrrole synthesis according to Aponick and Akai. REVIEWSHomogeneous Gold-Catalyzed Cyclization Reactions of Alkynes Scheme 32. Formationo fp yrroles via 5-exo-dig cyclization with acationic Au(I) catalyst.Scheme 33. Formationo fhomoallylic pyrroles via aza-Claisen rearrangement according to Gagosz. REVIEWSHomogeneous Gold-Catalyzed Cyclization Reactions of Alkynes Scheme 58. Au-catalyzed hydroamination in the total synthesis of (À)-Quinocarcin.Scheme 59. Reactionb etween o-alkynylbenzaldehydes and anilines under AuCl catalysis.Scheme60. Intramolecular hydroamination and transfer hydrogenation. REVIEWSHomogeneous Gold-Catalyzed Cyclization Reactions of Alkynes Scheme 79. Generation of ac ontact ion pair with retention of stereochemistry,a nd the unobserved sigmatropicr earrangement with inversion of stereochemistry.Scheme 80. Au(III)-catalyzed cycloisomerization with formation of dihydrothiazoles.Scheme81. Au(I)-catalyzed generation of an Au-carbene.

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Gold-Catalyzed Tandem 1,3-Migration/[2 + 2] Cycloaddition of 1,7-Enyne Benzoates to Azabicyclo[4.2.0]oct-5-enes

Abstract: A synthetic method that relies on gold(I)-catalyzed tandem 1,3-migration/[2 + 2] cycloaddition of 1,7-enyne benzoates to prepare azabicyclo[4.2.0]oct-5-enes is described.

Cited by 113 publications

References 53 publications

New developments in gold-catalyzed manipulation of inactivated alkenes

New developments in gold-catalyzed manipulation of inactivated alkenes

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

Homogeneous Gold‐Catalyzed Cyclization Reactions of Alkynes with N‐ and S‐Nucleophiles

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