Payne rearrangements, aza

Aza-Payne rearrangement of optically active A-aryl(alkyl)sulfonyl-substituted 2-aziridinemethanols to corresponding epoxysulfonamides 98CSR145. 

The aza-Payne rearrangement and its use as a synthetically valuable equilibration process has been reviewed. Unusual diazadioxabicyclo[2.2.2]octanes (352) have been obtained by the acid-catalysed rearrangement of A -quinazolinonyl- and A -phthalimido-aziridines derived from 3-phenylcyclohex-2-enol. ° A probable mechanism is outlined in Scheme 108. A-Acyl-2,2-dimethylaziridines have been isomerized by sodium iodide into three isomers whose yields appear to depend... 

Aza-Payne rearrangements, 60, 1 Azaphenanthrenes, synthesis by photocyclization, 30, 1 Azides, synthesis and rearrangement of, 3, 9... 

The aza-Payne rearrangement of activated /V-Ts- , -disubsfiluted-aziridinemeth-anols, induced by NaOH in the mixed solvent r-BuOH-H20-THF (4 5 1) or NaH in the mixed solvent THF-HMPA (10 1), and also some iV-Boc-a,a-disubstituted-aziridinemethanols with the latter reagent-solvent combination, provides the corresponding epoxides in up to 99% yield.20... 

Hydroxymethylaziridine 67 undergoes ring opening in the presence of either carbon- or heteroatom-based nucleophiles upon treatment with 2 equiv of potassium hydride to provide the t)7aminoalcohol derivative 69. The key step of the reaction is considered to be an aza-Payne rearrangement of the deprotonated aziridine methanol to the... 

A new example of the aza-Payne rearrangement has been used to prepare a-hydroxyaziridines <2005OL3267>. The epoxy imine 673 is prepared by a sequential epoxidation and imination. Reaction of 673 with a series of alkyllithium reagents initially adds to the imine which then does an aza-Payne rearrangement to form the hydroxy-aziridine 674 (Scheme 165). While the method generally suffers from poor yields, the one-step nature of the transformation lends greatly to its appeal. 

The Lewis acid-catalyzed aza-Payne rearrangement was utilized in the total synthesis of ep/-7-deoxypancratistatin by T. Hudlicky and co-workers. The 2,3-aziridino alcohol was treated with f-BuLi, to generate the epoxy amide that was trapped with piperonyl bromide. 

Ibuka, T., Nakai, K., Akaji, M., Tamamura, H., Fujii, N., Yamamoto, Y. An aza-Payne rearrangement-epoxide ring opening reaction of 2-aziridinemethanols in a one-pot manner a regio- and stereoselective synthetic route to diastereomerically pure N-protected 1,2-amino alcohols. Tetrahedron 1996, 52, 11739-11752. 

Rinner, U., Siengalewicz, P., Hudlicky, T. Total synthesis of epi-7-deoxypancratistatin via aza-Payne rearrangement and intramolecular... 

In the so-called aza-PAYNE rearrangement [12], (aminomethyl)oxiranes A are transformed to (hydroxymethyl)aziridines B. However, if compounds A are treated with magnesium bromide in dioxane, isomers of B (of different ring size) are obtained (C). 

The same group also disclosed the synthesis of epz-7-deoxypaneratistatin via an aza-Payne rearrangement (254) (Scheme 7). Analogues of narciclasine (68), pan-crastistatin, and 7-deoxypancratistatin have been synthesized using modifications of the reported procedures as well as new methodologies (e.g. addition of indoles to oxiranes and aziridines derived from cyclohexadiene diols) (255-258). 

Figure 8.12 Aza-Payne rearrangement in solvolysis of fi-substituted cyclic amines.

Scheme 10.5 Aza-Payne rearrangement of the p-lartam-hased substrate. 

Scheme 10.3 Aza-Payne rearrangement of representative 2,3-epoxy amines.

Application of the aza-Payne rearrangement was reported for the construction of highly substituted pyrrolidines starting from allqmylated aziridinemethanols as the substrates.Thus, as described in Scheme 10.4. treatment of the stereospecifically prepared syn-16 in the case of R, H with dimethylsulfoxonium methylide initiated the structural transposition to furnish the intermediary all yl epoxide lnt-2 which further cyclized to epoxy pyrrolidine 17 in a one-pot manner. Aldiou die diastereomeric anti-16 experienced the same rearrangement, but the following cyclization was not possible due to trans relationship between the reacting two units. 

A recent interesting example in this area is the rearrangement of epoxy azide 18 which, on exposure to triethylphosphine and after liberation of nitrogen gas, underwent the aza-Payne rearrangement fScheme 10.51. In this case, EtgP was responsible for successful stabilization of the reactive nitrogen species by formation of an aza-ylide intermediate, enabling the direct synthesis of N—H aziridine 19. 

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