Item – Theses Canada

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OCLC number
1019459901
Author
Hili, Ryan Matthew.
Title
Unprotected Amino Aldehydes in Organic Synthesis.
Degree
Ph. D. -- University of Toronto, 2010
Publisher
Ottawa : Library and Archives Canada = Bibliothèque et Archives Canada, 2012.
Description
microfiches
Notes
Includes bibliographical references.
Abstract
<?Pub Inc> In 1908, H. Emil Fisher attempted to prepare glycinal, an unprotected amino aldehyde, which he found to be inherently unstable and prone to polymerization. This instability arises from the propensity of amines to condense with aldehydes. Accordingly, amino aldehydes require protection of the amine functional group. On the contrary, aziridines do not condense with aldehydes; the aziridine ring-strain precludes the formation of an iminium ion. Predicated upon this orthogonal reactivity, a stable class of unprotected amino aldehydes has been prepared, and an in-depth investigation into their chemical reactivity has been undertaken.1,2 Reactions designed to utilize both their nucleophilic (amine) and electrophilic (aldehyde) centres have demonstrated their capacity to forge multiple bonds in a single transformation, and have been implemented in the synthesis of complex heterocycles and cyclic peptides.* (1) Publications: a) Hili, R., Yudin, A. K. "Making carbon-nitrogen bonds in biological and chemical synthesis" 'Nature Chem. Biol '. 2006, '2', 284-287. b) Hili, R.; Yudin, A. K. "Readily available unprotected amino aldehydes" ' J. Am. Chem. Soc'. 2006, '128', 14772- 14773. c) Yudin, A. K., Hili, R. "Overcoming the demons of protecting groups with amphoteric molecules" 'Chem. Eur. J'. 2007, '13', 6538-6542. d) Hili, R.; Yudin, A. K. "Amphoteric amino aldehydes enable rapid assembly of unprotected amino alcohols" ' Angew. Chem. Int Ed'. 2008, '47', 4188-4191. e) Hili, R.; Baktharaman, S.; Yudin, A. K. "Synthesis of chiral amines using [alpha]-amino aldehydes" 'Eur. J. Org. Chem'. 2008, '31', 5201 - 5213. f) Baktharaman, S.; Hili, R.; Yudin, A. K. "Amino carbonyl compounds in organic synthesis'' ' Aldrichimica Acta', 2008, '41', 109 - 119. g) Hili, R.; Yudin, A. K. "Amphoteric amino aldehyde re-route the ' aza'-Michael reaction" 'J. Am. Chem. Soc'. 2009, '131', 16404 - 16406. h) Hili, R.; Yudin, A. K. "Macrocyclization of linear peptides enabled by amphoteric amino aldehydes" submitted 2009. (2) Patents: a) Yudin, A. K.; Hili, R. "Unprotected amino aldehydes and applications for same" ' WO patent No. 2008046232'. b) Yudin, A. K.; Hili, R. "Cyclic Peptide Synthesis using Unprotected Amino Aldehydes" 'US provisional patent No. 61160571'. *Please refer to dissertation for diagrams.
ISBN
9780494723746
0494723742