- Visible-light-mediated, nitrogen-centered radical amination of tertiary alkyl halides under metal-free conditions to form α-tertiary amines
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A mild and operationally convenient amino-functionalization of a range of tertiary alkyl halides by reaction with iminoiodinanes (PhINNs) and I2 has been developed. According to the mechanistic experiments described within, the reaction is spec
- Brueckner, Alexander C.,Hancock, Erin N.,Anders, Evan J.,Tierney, Matthew M.,Morgan, Heather R.,Scott, Kristina A.,Lamar, Angus A.
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supporting information
p. 4387 - 4392
(2016/06/06)
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- A versatile tripodal Cu(I) reagent for C-N bond construction via nitrene-transfer chemistry: Catalytic perspectives and mechanistic insights on C-H aminations/amidinations and olefin aziridinations
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A CuI catalyst (1), supported by a framework of strongly basic guanidinato moieties, mediates nitrene-transfer from PhI=NR sources to a wide variety of aliphatic hydrocarbons (C-H amination or amidination in the presence of nitriles) and olefins (aziridination). Product profiles are consistent with a stepwise rather than concerted C-N bond formation. Mechanistic investigations with the aid of Hammett plots, kinetic isotope effects, labeled stereochemical probes, and radical traps and clocks allow us to conclude that carboradical intermediates play a major role and are generated by hydrogen-atom abstraction from substrate C-H bonds or initial nitrene-addition to one of the olefinic carbons. Subsequent processes include solvent-caged radical recombination to afford the major amination and aziridination products but also one-electron oxidation of diffusively free carboradicals to generate amidination products due to carbocation participation. Analyses of metal- and ligand-centered events by variable temperature electrospray mass spectrometry, cyclic voltammetry, and electron paramagnetic resonance spectroscopy, coupled with computational studies, indicate that an active, but still elusive, copper-nitrene (S = 1) intermediate initially abstracts a hydrogen atom from, or adds nitrene to, C-H and C=C bonds, respectively, followed by a spin flip and radical rebound to afford intra- and intermolecular C-N containing products.
- Bagchi, Vivek,Paraskevopoulou, Patrina,Das, Purak,Chi, Lingyu,Wang, Qiuwen,Choudhury, Amitava,Mathieson, Jennifer S.,Cronin, Leroy,Pardue, Daniel B.,Cundari, Thomas R.,Mitrikas, George,Sanakis, Yiannis,Stavropoulos, Pericles
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supporting information
p. 11362 - 11381
(2014/09/17)
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- Iron-catalyzed efficient intermolecular amination of C(sp3)-H bonds with bromamine-T as nitrene source
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[Fe(N4Py)(CH3CN)](ClO4)2 can efficiently catalyze intermolecular nitrene insertion of sp3 C-H bonds with bromamine-T as the nitrene source, forming the desired tosylprotected amines with NaBr as the by-product.
- Wang, Haiyu,Li, Yuxi,Wang, Zhiming,Lou, Jun,Xiao, Yuling,Qiu, Guofu,Hu, Xianming,Altenbach, Hans-Josef,Liu, Peng
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p. 25287 - 25290
(2014/07/07)
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- Ligand-assisted, copper-catalyzed enantioselective benzylic amination
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Several classes of ligands, including α-amino acids, diamines, diphosphines, bis-oxazolines, and diimines, support efficient copper-catalyzed amination of benzylic hydrocarbons by anhydrous chloramine-T. Catalysts derived from homochiral ligands, particularly chiral diimines, effect aminosulfonation with low to moderate enantioselectivity.
- Barman, Dipti N.,Nicholas, Kenneth M.
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supporting information; experimental part
p. 1815 - 1818
(2010/09/07)
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- Hydrous zinc halide-catalyzed aminosulfonation of hydrocarbons
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Benzylic and allylic hydrocarbons are selectively converted to the corresponding sulfonamides by a ZnBr2-H2O-catalyzed reaction with PhI=NTs; saturated adamantane is aminosulfonated at the tertiary C-H bond. The Royal Society of Chemistry.
- Kalita, Biswajit,Lamar, Angus A.,Nicholas, Kenneth M.
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supporting information; experimental part
p. 4291 - 4293
(2009/03/12)
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- Efficient copper-catalyzed benzylic amidation with anhydrous chloramine-T
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Benzylic hydrocarbons are selectively converted to the corresponding sulfonamides by the [Cu(CH3CN)4]PF6-catalyzed reaction with anhydrous TolSO2NNaCl (chloramine-T). Under the same conditions, representative ethers are also α-amidated; olefins produce allyl sulfonamides, aziridines, and/or β-chloro sulfonamides.
- Bhuyan, Ranjana,Nicholas, Kenneth M.
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p. 3957 - 3959
(2008/02/11)
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- A CHEMOSELECTIVE CONVERSION OF ALKYL AND ARYL AZIDES TO AMINES WITH SODIUM HYDROGENTELLURIDE
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By treatment with sodium hydrogentelluride in ethanol/ether at room temperature, alkyl and aryl azides are easily converted to the corresponding primary amines in good yields.
- Suzuki, Hitomi,Takaoka, Koji
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p. 1733 - 1736
(2007/10/02)
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- REACTIONS OF N-SULFINYL-p-TOLUENESULFONAMIDE WITH ALCOHOLS
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N-Sulfinyl-p-toluenesulfonamide (1) reacted with triaryl- and diarylmethanols to give predominantly N-substituted sulfonamides and SO2 presumably via carbonium ion intermediates.When carbonium ion forming alcohols, such as t-BuOH and Ph2C(Me)OH, were used, the predominant products were alkenes and p-toluenesulfonamide.Allylic alcohols afforded N-substituted sulfonamides, along with dienes and p-toluenesulfonamide.Alcohols wich could not predictably give relatively stable intermediate carbonium ions, gave either dialkyl sulfites or dialkyl ethers, along with p-toluenesulfonamide.In one case, namely with 9-phenylfluorenol, the 1:1 adduct with 1 (an amidosulfite) was isolated.A mechanism for the reaction is proposed.
- McFarland, John W.,Schut, Dirk,Zwanenburg, Binne
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p. 389 - 393
(2007/10/02)
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