Skeletal Rearrangement of <i>O</i>‐Propargylic Formaldoximes by a Gold‐Catalyzed Cyclization/Intermolecular Methylene Transfer Sequence

Nakamura, Itaru; Gima, Shinya; Kudo, Yuji; Terada, Masahiro

doi:10.1002/ange.201501856

Cited by 10 publications

(3 citation statements)

References 49 publications

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“…[76][77] The author suggest that K 2 CO 3 plays crucial role to decompose the in situ generated H 2 O 2 which interfere with stabilization of less stable radical species 9B and/or 9C. Then, an intermolecular N-methyl transfer [78] (path a) from radical cation 9B or 9C affords Nmethylamine biradical species 9D, subsequently which converted into target product 10 a by through radical addition cyclization to alkynyl triple bond. Alternately, prior to N-methyl transfer, an intramolecular radical addition reaction to alkyne moiety in 9B or 9C may provide Cu-DHII indolium 9E which subsequently underwent an intermolecular N-methyl transfer to afford 10 a (path b).…”

Section: Cu(ii)-catalyzed 12-diaminationmentioning

confidence: 99%

Transition‐Metal‐Catalyzed 1,2‐Diaminations of Olefins: Synthetic Methodologies and Mechanistic Studies

Kumar

2023

Chemistry An Asian Journal

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1,2‐Diamines are synthetically important motifs in organo‐catalysis, natural products, and drug research. Continuous utilization of transition‐metal based catalyst in direct 1,2‐diamination of olefines, in contrast to metal‐free transformations, with numerous impressive advances made in recent years (2015‐2023). This review summarized contemporary research on the transition‐metal catalyzed/mediated [e.g., Cu(II), Pd(II), Fe(II), Rh(III), Ir(III), and Co(II)] 1,2‐diamination (asymmetric and non‐asymmetric) especially emphasizing the recent synthetic methodologies and mechanistic understandings. Moreover, up‐to‐date discussion on (i) paramount role of oxidant and catalyst (ii) key achievements (iii) generality and uniqueness, (iv) synthetic limitations or future challenges, and (v) future opportunities are summarized related to this potential area.

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Section: Cu(ii)-catalyzed 12-diaminationmentioning

confidence: 99%

Transition‐Metal‐Catalyzed 1,2‐Diaminations of Olefins: Synthetic Methodologies and Mechanistic Studies

Kumar

2023

Chemistry An Asian Journal

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“…Nakamura and co‐workers discovered a skeletal rearrangement of O ‐propargylic formaldoximes 50 , catalyzed by PPh 3 AuNTf 2 (Scheme ) 55. The mechanism consists of a cyclization/intermolecular CC bond formation/disconnection sequence.…”

Section: N‐nucleophilesmentioning

confidence: 99%

“…After Au‐catalyzed 5‐ endo ‐ dig cyclization, a trace amount of water present in the reaction mixture attacks the in situ formed iminium species 51 and then consecutive attack of the nucleophilic vinylgold moiety onto the iminium moiety results in oligomers 54 . Protodeauration, caused by trace amounts of water, and assisted elimination of non‐methylenated isoxazoline 56 then results in the release of methylenated isoxazolines 59 55. Shin and co‐workers also reported on an Au‐catalyzed dihydroisoxazole synthesis 56…”

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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Rhodium‐Catalyzed Cycloisomerization of 2‐Alkynyl‐N′‐arylidenebenzohydrazides through exo‐Carboamination

Matsuda

2016

Asian J Org Chem

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Skeletal Rearrangement of O‐Propargylic Formaldoximes by a Gold‐Catalyzed Cyclization/Intermolecular Methylene Transfer Sequence

Cited by 10 publications

References 49 publications

Transition‐Metal‐Catalyzed 1,2‐Diaminations of Olefins: Synthetic Methodologies and Mechanistic Studies

Transition‐Metal‐Catalyzed 1,2‐Diaminations of Olefins: Synthetic Methodologies and Mechanistic Studies

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

Rhodium‐Catalyzed Cycloisomerization of 2‐Alkynyl‐N′‐arylidenebenzohydrazides through exo‐Carboamination

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