Nitrogen stereochemistry

The first elucidation of the nitrogen stereochemistry of a bisbenzylisoquinoline N-oxide alkaloid (see calafatine N-oxides, Section H,C,10) was made possible by NOEDS. A procedure was developed that systematically interconnects all protons, allowing complete structure determination (54). A previous attempt to prove the stereochemistry of the epimeric calafatine N-oxides had given an erroneous result due to inadequate decoupling data (59). 

Step 8 Sn2 displacement of the mesylate establishes the correct nitrogen stereochemistry. 

Kfen, V., NSmecek, J. and Pfikrylova, V. (1995) Assignment of nitrogen stereochemistry of agroclavine and elymoclavine 6-N-oxides. Collect. Czech. Chem. Commun., 60, 2165-2169. 

The chemistry and stereochemistry of aminoboranes containing the siLicon—nitrogen—boron linkage have been the subject of numerous studies. Many of these compounds are useful precursors to other B—N systems including diboryl-amines (45) and B—H substituted aminoboranes (46). A series of... 

The results observed in the oxidation of alkaloids which indicated something of the stereochemistry required for oxidation and prompted studies on model systems can now be interpreted more confidently. However, care must be used when basing steric differentiation on mercuric acetate oxidation studies since conditions must be employed which avoid epimerization at carbons alpha to the nitrogen. 

It is not known whether the amine assists the elimination of the nitrogen, but that the iminium salt retains its stereochemistry has been demonstrated (709). When a mixture of 68 and 69of 1 5 ratio is treated with diazomethane, the ratio of 70 71 obtained in 75% yield and determined spectroscopically was still 1 5. The traw-N-isopropyl-N-methylisobutylidinium perchlorate (69) was prepared by alkylation of an aldimine salt with diazomethanc and... 

The most general method for synthesis of cyclic enamines is the oxidation of tertiary amines with mercuric acetate, which has been investigated primarily by Leonard 111-116) and applied in numerous examples of structural investigation and in syntheses of alkaloids 102,117-121). The requirement of a tram-coplanar arrangement of an a proton and mercury complexed on nitrogen, in the optimum transition state, confers valuable selectivity to the reaction. It may thus be used as a kinetic probe for stereochemistry as well as for the formation of specific enamine isomers. 

Several factors influence the diastereoselectivity of the Pictet-Spengler condensation to form 1,3-disubstituted and 1,2,3-trisubstituted tetrahydro-P-carbolines (39 and 40, respectively). The presence or absence of an alkyl substituent on the nitrogen of tryptophan has a large influence on the relative stereochemistry of the tetrahydro-P-carboline products formed from a condensation reaction with an aldehyde under various reaction conditions. 

The regioselective ring-opening of vinyloxiranes by nitrogen nucleophiles offers an attractive route to vie-amino alcohols, compounds of much recent interest. As with oxygen nucleophiles, the stereochemistry of the reaction can be controlled by choice of reaction conditions aminolysis of 25, for example, affords anti-amino alcohol 26 in excellent yield and diastereoselectivity (Scheme 9.21) [48, 96, 97], and... 

On this basis, the bent nitrogens with square pyramidal structures like Ir(NO)Cl2(PPh3)2 are assigned to the M111 (d6) oxidation state in keeping with other examples of this stereochemistry, such as RhCH3I2(PPh3)2. 

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