Asymmetric Dihydroxylation and Aziridination of Allenes and Related Chemistry

A novel method for asymmetric synthesis of α-hydroxy ketone with excellent regio- and stereoselectivity has been established by the systematic investigation of asymmetric dihydroxylation of allenes. The efficiency of kinetic resolution of racemic allenes was also investigated by using the AD reaction on both 1,3-disubstituted and trisubstituted allenes. Steric effects, electronic effects and allene substitution are also discussed. Aziridines were formed by copper-catalyzed intramolecular nitrene addition to alkenes. The carbamate group was used as the tether between the alkene and the nitrene. Subsequent nucleophilic attack of the aziridine was accomplished using RSH, R2NH, N3-,or ROH as the nucleophile. This addition was found to be regio- and stereoselective. This methodology has provided a new strategy for the stereoselective construction of three adjacent functional groups, in particular the 1,2 diamino-3-hydroxy unit. The rhodium-catalyzed intramolecular aziridination of allenic N-sulfonyloxy carbamates has been established. Efficient ring opening of these bicyclic compounds may provide synthetic utility in organic chemistry. The intramolecular aziridination of allenic sulfamate esters was tested on a single example to afford in situ a ring opened product.

Name thesis:degree_name

PhD

Grantor dc:publisher

Brigham Young University - Provo

Author dc:creator

• Liu, Renmao

• asymmetric dihydroxylation
• aziridination
• allenes
• alkenes
• α-hydroxy ketone
• aziridines
• Biochemistry
• Chemistry

Language dc:language

English

Repository record dc:identifier

https://scholarsarchive.byu.edu/etd/899

OAI identifier oai:identifier

oai:scholarsarchive.byu.edu:etd-1898