Efficient Copper-Catalyzed Benzylic Amidation with Anhydrous Chloramine-T

Abstract

Benzylic hydrocarbons are selectively converted to the corresponding sulfonamides by the [Cu(CH(3)CN)(4)]PF(6)-catalyzed reaction with anhydrous TolSO(2)NNaCl (chloramine-T). Under the same conditions, representative ethers are also alpha-amidated; olefins produce allyl sulfonamides, aziridines, and/or beta-chloro sulfonamides.

Halogenative kinetic resolution of β-amido alcohols: chiral BINAP-mediated SN2 displacement of hydroxy groups by chlorides with inversion of stereochemistry

“…The cis-stereochemistry of the b-amido chloride (1R,2S)-cis-2 was confirmed by comparing its 1 H and 13 C NMR values with the literature reports. 9,12 The trans-chloride was not observed in the reaction. The strong electron-withdrawing nature of sulfonamide group prevented the neighbouring group participation ability of the amino group which resulted in an optically active cis-chloride with an inversion of stereochemistry.…”

“…1,21.7,24.5,28.3,33.3,55.1,64.1,127.0,129.9,138.6,143.6;HRMS (ESI): m/z calcd for C 13 3.30 (td,J = 9.6,9.2,3.6 Hz,1H),4.70 (br s,1H),2H),1H), 7.91 (d, J = 7.6 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ): d 24.0, 24. 8,32.1,33.6,59.9,73.5,127.3,129.3,132.9,140.6;HRMS (ESI): m/z calcd for C 12 8, 32.1, 33.6, 55.7, 59.8, 73.5, 114.5, 129.4, 132.1, 163. 24.5, 28.3, 33.3, 55.1, 55.8, 64.1, 114.5, 129.2, 133.2, 163 …”

Visible‐Light‐Catalyzed Direct Benzylic C(sp3)–H Amination Reaction by Cross‐Dehydrogenative Coupling

“…[1] The nitrogen source in the majority of these reactions is am etalcatalyzed nitrenoid that inserts into the C(sp 3 )-H bond using either organic azides, [2] iminoiodanes [3] or haloamine derivatives (ZNNaX) [4] as nitrene precursors.While non-selectivity, low yield, and employment of ah ighly electrophilic nitrene source typically marked the former processes,u se of hypervalent iodine reagents and the generation of astoichiometric amount of environmentally non-benign iodobenzene remains am ajor drawback of the later approaches.A lthough, an alternative approach of generating nitrene and its insertion into the C À Hb ond by rhodium-catalyzed decomposition of N-tosyloxycarbamates [5] overcomes some of these problems, the high costs of the rhodium metal and its non-recyclability limit its use.F urthermore,h ypervalent N-trifluoromethylsulfonylimino-l 3 -bromane [6] has also been used as an active organo nitrenoid species for the C-H amination reaction but this strategy produces as toichiometric amount of trifluoromethylbromobenzene as ab y-product. Ad ivergent regioselectivity of intramolecular C-H amination has also been reported by generating nitrenoid species from two differently engineered variants of P450BM3 where one is favoring amination of benzylic C À Hb onds and the other is favoring homo-benzylic C À Hb onds, [7] but this approach is highly substrate specific.…”

Enantioselective CH Amination

“…Intramolecular CÀH amination is often observed as a side reaction of Cu- [30] and Rh- [31,32] catalyzed aziridination of olefins. Readily available iminoiodinanes of formula PhI ¼ NR (R ¼ Ts, Ns) are generally utilized as the source of nitrogen, but the employment of commercially available chloro-or bromamine-T [34,37,[41][42][43][44] or arylazides [35,45] has also been reported. Readily available iminoiodinanes of formula PhI ¼ NR (R ¼ Ts, Ns) are generally utilized as the source of nitrogen, but the employment of commercially available chloro-or bromamine-T [34,37,[41][42][43][44] or arylazides [35,45] has also been reported.…”