I⁻/TBHP catalyzed C_sp3–N/C_sp2–N bond formation via oxidative coupling with benzophenone imine in water

Abstract

An I−/TBHP catalyzed oxidative amination with benzophenone imine under environmentally benign conditions was developed to afford primary amines and amides.

α,β‐Double Electrophilic Addition of Allene‐1,3‐Dicarboxylic Esters for the Construction of Polysubstituted Furans by KI/tert‐Butyl Hydroperoxide (TBHP)‐Promoted Oxidative Annulation

“…[12k, 14] Based on these observations, we speculate that the iodite species[ IO 2 ] À may be the key oxidant in this reaction. Based on the resultsd escribed above and previous reports, [12][13][14][15] ah ypothetical mechanism is proposed in Scheme4. Initially,t he oxidation of I À with TBHP easily generatesI 2 and OH À ,a nd subsequently transformsi nto hypoiodite [IO] À , which can be further oxidized by TBHP to form the iodite [IO 2 ] À .…”

“…Interestingly,t he reaction of unsymmetrical b-diketone 4m with 2a resulted in ar egioisomeric mixture of 5ma and 5mb in 75 %y ield (5ma/5mb= 5:1; Table 3, entry 13). Moreover, sub-strates containing naphthalene, pyridine, furan,a nd thiophene moieties were also suitable for this reaction, affording the corresponding products in moderate to good yields ( Table 3, entries [14][15][16][17]. Finally,t of urthere xtend the reactions cope, 3oxo-3-arylpropanenitriles, b-keto sulfone, and diethyl( 2-oxo-2phenylethyl)phosphonate were also investigated under the optimal conditions.…”

“…According to several recent reports, the in situ generated base and I 2 from aI À / TBHP system would be further transformed into hypoiodite and iodite species ([IO] À and [IO 2 ] À )i nt he presence of excess TBHP,w hich could be the keyo xidant involved in the oxidative annulation (Scheme 4). [12][13][14] Hence, we next envisaged whether hypoiodite ([IO] À )a nd/or iodite ([IO 2 ] À )w ere the actual oxidant species. However,b ecause the reaction of 6a gave no desired product 5a in the presence of as toichiometric amount of I 2 and KOH ([IO] À generated in situ;T able 4, entry 5), this sug-gested that [IO] À was not the actual oxidant species.…”

Synthesis of Hypervalent Iodine(III) Reagents Containing a Transferable (Diarylmethylene)amino Group and Their Use in the Oxidative Amination of Silyl Ketene Acetals

“…[7] Thus,t he development of an ew method that enables the introduction of ar eadily modifiable nitrogen-containing functional group into an organic molecule utilizing hypervalent iodine reagents continues to be ac hallenging task. [10] Benzophenone imine has been used as an aminating reagent in transition-metal catalyzed amination [11] and catalytic C À Ha mination, [12] and the resulting aminated products can be easily hydrolyzed to give primary amines.Inaddition, N-stannyl benzophenone imine has been applied to aradical alkylation reaction. [13] Meanwhile,b enzophenone iminederived oxime derivatives function as electrophilic aminating reagents,w hich enables the amination of alkynyl copper reagents, [14a] Grignard reagents, [14b] and organoboron compounds with ac opper catalyst.…”

Site‐Specific S‐Allylation of α‐Enolic Dithioesters with Morita‐Baylis‐Hillman Acetates at Room Temperature: Precursor for Thiopyrans

“…Based on the literature reports, [26] and our experimental observations, a plausible mechanism has been given in Scheme The structures of all the new compounds were assigned by satisfactory spectroscopic ( 1 H, 13 C NMR, and HRMS) studies, and unambiguously established by the single crystal X-ray diffraction analysis of two representative compounds 3 c and 6 b (see Figure 1 and the Supporting Information). [27]…”