Tosylimino group

Such metal-complexed nitrenes were also generated by the reaction of (tosyliminoio-do)benzene (106) with Mn(m)- or Fe(n)-tetraphenylporphyrin, 107, in a mimic of cytochrome P-450 but with a tosylimino group instead of an oxygen atom on the metals (108) [179]. It was able to functionalize cyclohexane solvent, by nitrogen insertion into a C-H bond to form 109. Furthermore, the metalloporphyrins also catalyzed an intramolecular nitrogen insertion converting 110 into 111 [180]. 

As an analog, 1,3,5-trithiane 1-tosylimide 154 was synthesized by the reaction between chloroamine-T and 1,3,5-trithiane in DMF. After pouring the reaction solution into cold water, the precipitate, recrystallized from acetonitrile, was proven by X-ray crystallography to have the tosylimino group equatorially oriented on a 1,3,5-trithiane chair conformer (Scheme 40) <1994J(P2)1439>. The sodium salt 156 reacted further with NaH/Mel in dimethylformamide (DMF) but delivered a product mixture of ( )-155 and meso-155. Thus the authors failed to break the symmetry of 154 and, as part of their asymmetric synthesis program, to deliver enantiomerically enriched products (Scheme 40) <1995J(P1)313>. 

The glutamic moiety of TNP-351, a pyrrolo[2,3-d]pyrimidine glutamic acid derivative, and related compounds have been transformed into their A-co-masked ornithine analogs which show remarkable antifolate activity <00CPB1270>. The reaction of the heterocyclic enamine 77 with tosyl azide leads to the tosylimino derivative of 1,2,4-triazolo[l, 5-a]pyrimidine 79. Extrusion of nitrogen from the primary adduct 78 is followed by a 1,2-shift of a methyl group to yield 79 <00JHC195>. 

Copper-catalyzed reactions of [(tosylimino)iodo]benzene with unsaturated compounds sometimes lead to tosylamidation. Examples include conversions of silyl enol ethers to a-tosylamido ketones [173], and tosylamidation of allylic silanes with loss of the silyl group [190] (Scheme 69). 

The allylation of a-iV-tosylimino esters, highly activated imines, proceeds by catalytic use of a Lewis acid. Tol-BINAP-Cu(l) complexes are effective catalysts of asymmetric allylation of these imines with allylsilanes (Equation (28)).124 125 The presence of an aryl group at the position j3 to silicon improves the enantioselectivity. 

Allylations. Catalyzed allylation of a-iodo acetals with leaving group dependence on the Lewis acid has been reported. Formation of N-tosyl allylamine by reaction of an allylsilane with (A -tosylimino)phenyliodinane is promoted by Cu(OTf)j. Halide displacement of a polyhalide" occurs in the presence of CuCl. 

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