Synthesis and catalytic applications of aziridine-containing scaffolds.
Contributors: University of Toronto.  Dept. of Chemistry.
Published: 2005
Language: eng
Number of pages: 372
Subjects: Advisor: Andrei Yudin
Description: The third project, described in Chapter 3, explored the dimerization of N-H aziridines using Lewis acid catalysts. It was found that in the presence of Yb(OTf)3 and acetoacetates, polymerization was suppressed, and a broad range of 3-[trans-2-(7-aza-bicyclo[4.1.0]hept-7-yl)-cyclohexylamino]-2-butenoates were formed in excellent yields and complete Z selectivity via ring-opening of 7-azabicyclo[4.1.0]heptane.The focus of this thesis is (a) the synthesis and applications of aziridine-derived P,N ligands and (b) the formation of carbon-nitrogen bonds involving aziridines catalyzed by transition metal complexes or Lewis acids. Three projects were examined; the first project, detailed in Chapter 1, involved the ring-opening of aziridines with dialkyl and diarylphosphines as nucleophiles, yielding P,N ligands with a cyclohexane backbone. These ligands were applied to catalytic reactions such as Suzuki coupling and allylic alkylation, exhibiting high reactivity and selectivity.The second project, described in Chapter 2, dealt with the metal-catalyzed coupling of N-H aziridines with aryl and alkenyl bromides as well as aryl and alkenyl boronic acids to form N-aryl and N-alkenyl aziridines in high yields and excellent selectivity. Through the use of such catalytic procedures, a wide variety of new N-alkenyl aziridines were synthesized, which were further transformed through thermal rearrangements.
Notes: Thesis (Ph.D.)--University of Toronto, 2005.

Electronic version licensed for access by U. of T. users.

Source: Dissertation Abstracts International, Volume: 66-06, Section: B, page: 3134.