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oai:www.ideals.illinois.edu:2142/84258 2023-07-11 col_2142_5131 col_2142_14789 com_2142_5130 com_2142_14788 com_2142_8903

Denmark, Scott E. Heemstra, John Richard, Jr 2015-09-25T22:13:41Z 2015-09-25T22:13:41Z 10000-01-01 2007 2007 Additionally, the use of the silicon tetrachloride---chiral phosphoramide system has proven a competent catalyst for highly selective vinylogous aldol reactions between dienolates derived from a variety of alpha,beta-unsaturated carbonyl compounds to aldehydes. These reactions provided high levels of gamma-site selectivity for a variety of substitution patterns on the dienyl unit. Both ketone- and morpholine amide-derived dienol ethers afforded excellent enantio- and diastereoselectivity in the addition to conjugated aldehydes. Although ketone-derived dienolate did not react with aliphatic aldehydes, amide-derived dienolates were found to undergo addition at reasonable rates affording high yields of vinylogous aldol product. The enantioselectivity achieved with the morpholine derived-dienolate in the addition to aliphatic aldehydes was the highest afforded to date with the silicon tetrachloride---chiral phosphoramide system. Furthermore, the ability to cleanly convert the morpholine amide to a methyl ketone was demonstrated. Made available in DSpace on 2015-09-25T22:13:41Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 3269914.pdf: 9569141 bytes, checksum: 8fbb1397b55a38358d3060312850f527 (MD5) Previous issue date: 2007 Embargo set by: Seth Robbins for item 85539 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs U of I Only 373 p. Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2007. http://hdl.handle.net/2142/84258 (MiAaPQ)AAI3269914 eng Chemistry, Organic Studies in Asymmetric Catalysis: Lewis Base catalyzed/Lewis Acid Mediated Aldol Reactions of Ketone- and Amide Derived Nucleophiles text Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.