Nitrogen-Transfer Reactions

Even though the coupHng reactions as investigated are only of achiral nature, there is an important precedence in asymmetric catalysis Rossen and Pye at Merck employed the planar-chiral bisphosphine PHANEPHOS to attempt a Id- 

As a different type of amination, the intermolecular hydroamination of nor-bornene with aniline was carried out with preformed Ir complexes 29 and 30 bearing bidentate ACTC ligands [15]. As it is commonly the case for the generation of such complexes, the catalyst precursors were isolated as an inseparable mixture of the respective cis- and trans-isomers. At 60 °C, only traces of the desired hydroamination product could be detected, and moderate enantioselectiv-ities of 51 and 70% ee were determined for catalysts derived from the cyclohexyl derivative 29 and the ferf-butyl derivative 30, respectively. Still, a significant improvement in rate is required to transform the present chiral catalyst system into a truly useful synthesis. 

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In 1983, Groves and Takahashi demonstrated that a nitrido-Mnvporphyrin underwent a nitrogen-transfer reaction via a tV-trifluoroacetylnitrenoid species to give an aziridine, when it was treated with trifluoroacetic anhydride (TFAA) in the presence of olefins (Scheme 31).141... 

Later, Carreira et al. reported that nitrido-Mnv(salen) also underwent a nitrogen-transfer reaction under similar reaction conditions.142 An asymmetric version of this reaction has been realized by using the chiral nitrido-Mnv(salen) (44) (Scheme 32).143 When trifluoroacetic acid... 

Nitrogen-transfer reactions of osmium imido species lead to cis diamines or amino alcohols. Reaction of 0s02(N-/-C4H9)2 [63174-13-0] with olefins produces vicinal diamines after reductive cleavage. Catalytic oxyamination of olefins using chloramine-T or AJ-chlor-AJ-argenocarbamates yields vicinal hydroxy toluenesulfonamides (112) or carbamates (113), respectively, which maybe deprotected to vicinal amino alcohols. 

Another useful method that has been investigated is the transfer of nitride from one metal center to a another. Thus, porphyrin manganese nitrides have been documented to participate in nitrogen transfer reactions to Cr -porphyrin and C -salen to furnish the corresponding Cr-nitrides (Eq. (11)) [19]. 

Copper Catalysts Copper is an excellent catalyst for nitrogen transfer reactions via copper-nitrene intermediates. Benzylic hydrocarbons are selectively converted to the corresponding sulfonamides [40]. The intermolecular amidation of saturated C—H bonds of cyclic ethers has been reported using TsNH2-PhI(OAc)2 or PhI=NTs as the nitrene source [41]. The copper-catalyzed amidation of unactivated sp3 C—H bonds adjacent to a nitrogen atom has also been achieved using tert-butyl hydroperoxide or... 

Advances in nitrogen transfer reactions involving aziridines 06ACR194. 

CARBON AND NITROGEN TRANSFER REACTIONS IN NUCLEOTIDE METABOLISM... 

In addition to the transphosphorylation reactions discussed in Chapter 4, there are several general types of carbon and nitrogen transfer reactions which also occur in purine and pyrimidine nucleotide biosynthesis and interconversion. Among these are one-carbon and phosphoribosyl transfer reactions, amino group transfer from glutamine and aspartate, and amide syntheses. In most of these processes carbon-nitrogen bonds... 

The carbon and nitrogen transfer reactions discussed here in the context of nucleotide metabolism are also common in amino acid metabolism and illustrate well the close relationship of these two areas. They are all discussed in Meister s study of amino acids 1). 

We had not, imtil recently, however, observed any of the nitrogen transfer reactions with LABs reported earlier by Hutchins. This summary will describe recently observed reactions of LABs, which display their multiple personalities (properties) and utility in synthetic organic chemistry. 

Figure 11. Nitrogen transfer reactions with sodium aziridinylborohydrides.

The synthesis of azidocyclopropanes has been accomplished with varying success via the nitrogen transfer reaction from toluene-p-sulphonyl azide to cyclopropylamine anions or by the addition of carbenes or carbenoids to vinyl azides. 

Watson IDG, Yu L, Yudin AK (2006) Advanees in nitrogen transfer reactions involving aziridines. Acc Chem Res 39 194—206... 

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