2013
DOI: 10.1002/anie.201301087
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Unveiling Latent α‐Iminocarbene Reactivity for Intermolecular Cascade Reactions through Alkyne Oxidative Amination

Abstract: The chemistry of reactive (electrophilic) metallocarbenes, primarily obtained by metal-catalyzed decomposition of adiazocarbonyl compounds, has been extensively developed and offers significant opportunity for strategic CÀC, CÀO, and CÀN bond formation through a variety of well-defined reaction mechanisms. [1] Given the prevalence of nitrogen atoms in biologically and pharmaceutically relevant molecules and the intrinsic electronic similarities between carbonyl and imine functional groups, the development of a… Show more

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Cited by 56 publications
(22 citation statements)
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“… 17 The Co( ii )-based MRC is among the few catalytic systems that are effective for amination of propargylic C–H bonds without affecting the electron-rich C C π bonds. 7d , 18 , 19 Functionalization of propargylic C–H bonds of both aryl-conjugated and alkyl-substituted alkynes led to the formation of the desired 5-membered cyclic sulfamides in high yields (entries 17–19). Moreover, the propargylic C–H bond of unprotected terminal alkynes could be also aminated selectively without interference from the acidic terminal C(sp)–H bond, as demonstrated by the formation of the cyclic sulfamide 2t in 89% yield.…”
Section: Resultsmentioning
confidence: 99%
“… 17 The Co( ii )-based MRC is among the few catalytic systems that are effective for amination of propargylic C–H bonds without affecting the electron-rich C C π bonds. 7d , 18 , 19 Functionalization of propargylic C–H bonds of both aryl-conjugated and alkyl-substituted alkynes led to the formation of the desired 5-membered cyclic sulfamides in high yields (entries 17–19). Moreover, the propargylic C–H bond of unprotected terminal alkynes could be also aminated selectively without interference from the acidic terminal C(sp)–H bond, as demonstrated by the formation of the cyclic sulfamide 2t in 89% yield.…”
Section: Resultsmentioning
confidence: 99%
“…Processes that invoke the interaction of am etal-nitrogen bond, as metallonitrenoid or metallonitrene, in the addition across the p-systema re not discussed here, but have been shownt og ive access to related intermediates. [5,6] While all the reactions discussed in this review can reasonably be viewed as proceeding through an a-imino metal carbene E synthon in ag eneral retrosynthetic sense, and may be referred to as such, it is importantt on ote that this brief analysis will not capture many important aspects of the reactivity or indeed always represent the actual intermediates involved. Twop oints in particulars hould be borne in mind in order to avoid an over-simplified pictureo ft he reactivity.F irst, both D and E have electrophilic character,s or eaction at the carbon center might occur either alongside or after elimination of the nucleofuge.…”
Section: Reactivity Basismentioning
confidence: 99%
“…135 This method has been exploited in an intermolecular cascade reaction through alkyne oxidative amination for the synthesis of seven-membered cyclic sulfamates 122 (Scheme 38). 136 A series of substrates 120 were used to obtain the corresponding enantioenriched products, the desired seven-membered cyclic sulfamates 122.…”
Section: Using Metallonitrene/alkyne Metathesismentioning
confidence: 99%