2013
DOI: 10.1002/ange.201304365
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Copper‐Catalyzed Intermolecular Regioselective Hydroamination of Styrenes with Polymethylhydrosiloxane and Hydroxylamines

Abstract: Scheme 1. Working hypothesis. Bz = benzoyl, L = ligand.

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Cited by 115 publications
(43 citation statements)
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“…It is worth noting that the originally proposed [6] two-step regeneration of {P^P}Cu I hydride through salt metathesis of 6 with LiOtBu base and transmetalation of the thus formed {P^P}Cu(OtBu) 2 with hydrosilane 1c is found energetically inaccessible ( Figure S16 in the Supporting Information) in the presence of the direct transformation shown in Figure 9. Figure 6.…”
Section: Regeneration Of {P^p}cu I Hydride From {P^p}cu I Benzoatementioning
confidence: 98%
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“…It is worth noting that the originally proposed [6] two-step regeneration of {P^P}Cu I hydride through salt metathesis of 6 with LiOtBu base and transmetalation of the thus formed {P^P}Cu(OtBu) 2 with hydrosilane 1c is found energetically inaccessible ( Figure S16 in the Supporting Information) in the presence of the direct transformation shown in Figure 9. Figure 6.…”
Section: Regeneration Of {P^p}cu I Hydride From {P^p}cu I Benzoatementioning
confidence: 98%
“…Unfortunately, all the efforts to localiset he associated TS structure have not been successful, but examination of the reaction path thoroughly by meanso fachain-of-state method firmly indicates that reductiveamine elimination at 7 has an only marginal barrier,i fa ta ll, to overcome,h ence it proceeds almosti nstantaneously.O verall,asmooth, kinetically affordable pathway for undesired 3 + 1b!6 + HNMe 2 conversion has been located that comprises af irst intramolecular S N 2c leavage of the NÀOb ond (DG°= 26.3 kcal mol À1 relative to { 1 = 2 3dim + 1b}, Figure 10), to be followed by highly rapid reductivea mine eliminationf rom an intervening and highly reactive {P^P}Cu III intermediate 7, thus reflectingt he well-documented aptitude of 3 to engage in performance-limiting reduction of the electrophilica mination reagent. [6,7] Further attemptsd evoted upon locating ap roper TS structure for the concerted attack of the nucleophilic CuÀHl inkage at the Nc entre of the amine electrophile to be accompanied with NÀOb ond disruption have not been successful. However, ar easonablya pproximateT S( Figure S15 in the SupportingI nformation)i ss een to be above TS[3 1 ·AÀ7]b ya nother 19.8 kcal mol À1 ,such that the concerted pathway can confidently be discardeda se nergetically viable alternative to the operative twostep process.…”
Section: Reduction Of the Benzylamine Ester By {P^p}cu I Hydridementioning
confidence: 99%
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“…In 2013, the groups of Miura/Hirano 11 a and Buchwald 11 b reported independently on a mechanistically novel approach for formal hydroamination employing upon a regiocontrolled hydrometalation of an olefin functionality and subsequent C–N bond formation through Umpolung electrophilic amination. The intermolecular reaction of vinylarenes with a hydride delivered from a silane and an electrophilic amino group from a hydroxylamine derivative, rather than an amine N–H bond, in the presence of a diphosphine copper compound gives rise to amines in excellent yields and enantio-/regioselectivities under mild conditions.…”
Section: Introductionmentioning
confidence: 99%