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oai:www.ideals.illinois.edu:2142/16534 2023-07-10 col_2142_14789 col_2142_5131 com_2142_14788 com_2142_8903 com_2142_5130

Denmark, Scott E. Denmark, Scott E. Katzenellenbogen, John A. White, M. Christina Suslick, Kenneth S. Xie, Min 2010-06-29T00:59:57Z 2010-06-29T00:59:57Z 2012-06-29T10:00:14Z 2010-06-29T00:59:57Z The chemistry of nitroalkenes and nitroalkanes has been explored with regard to synthesis of nitrogen-containing heterocycles, including 3-sustituted azepanes and 1-azoniapropellanes. A general synthesis of 3-sustituted azepanes has been developed using nitroalkenes as building blocks. A novel, vinylogous, conjugate addition reaction of an acylsilane-derived dienol ether to nitroalkenes was discovered. Reaction conditions were optimized for a number of -substituted nitroalkenes. Nitro acylsilanes as the conjugate adducts were obtained in good to moderate yield. Nitro acylsilanes were converted to the corresponding enals through a photoinduced protodesilylation. Saturation of the olefinic portion of the enals and subsequent reductive aminations afforded the 3-sustituted azepanes, which were protected as N-tosylamides. Using this streamlined process, a number of 3-sustituted azepanes were obtained in good yield. Efficient synthesis of chiral, enantiopure 1-azoniapropellanes as phase transfer catalysts has been developed. In the first method, the tandem [4+2]/[3+2] cycloaddition of nitroalkene was applied as the key step, wherein a chiral, enantiopure vinyl ether, a nitroalkene and a vinyl ketone were rapidly assembled. The resulting enantiopure nitroso acetals were then elaborated into 1-azoniapropellanes. Four azoniapropellanes were prepared using this method. Another method was developed using the conjugate addition of nitroalkanes to Michael acceptors as the key strategy. Stereochemical control was achieved by the application of Corey-Itsuno reduction of the nitro diketone intermediate. Starting from nitromethane and -chloropropiophenone, rapid access to 2,8-diphenyl-1-azoniapropellane and 2,8,9-triphenyl-1-azoniapropellane was accomplished . Item withdrawn by Mark Zulauf (zulauf@illinois.edu) on 2010-04-14T13:04:42Z Item was in collections: University of Illinois Theses & Dissertations (ID: 1) No. of bitstreams: 1 Min Xie dissertation.pdf: 2367315 bytes, checksum: 45c16aba7e185a9b346ee90a2a301a15 (MD5) Made available in DSpace on 2010-06-29T00:59:57Z (GMT). No. of bitstreams: 4 Xie_Min.pdf: 2368082 bytes, checksum: 496f2985307e3dce93d05ef507d2da1e (MD5) Min Xie dissertation.pdf: 2367315 bytes, checksum: 45c16aba7e185a9b346ee90a2a301a15 (MD5) 1_Xie_Min.pdf: 2369897 bytes, checksum: 1893046345bb36b97f440a1455c31af8 (MD5) license.txt: 4055 bytes, checksum: 9de97a6700165a0d0bd80b8935d69e40 (MD5) Item marked as restricted to the 'Administrator' Group (id=1) by William Ingram (wingram2@illinois.edu) on 2010-06-29T01:01:56Z Item is restricted until 2012-06-29T01:01:54Z Item reinstated by Sarah Shreeves (sshreeve@illinois.edu) on 2012-06-29T10:00:14Z Item was in collections: Dissertations and Theses - Chemistry (ID: 676) University of Illinois Dissertations and Theses (ID: 204) No. of bitstreams: 5 Xie_Min.pdf: 2368082 bytes, checksum: 496f2985307e3dce93d05ef507d2da1e (MD5) Min Xie dissertation.pdf: 2367315 bytes, checksum: 45c16aba7e185a9b346ee90a2a301a15 (MD5) 1_Xie_Min.pdf: 2369897 bytes, checksum: 1893046345bb36b97f440a1455c31af8 (MD5) license.txt: 4055 bytes, checksum: 9de97a6700165a0d0bd80b8935d69e40 (MD5) 1_Xie_Min.pdf.txt: 290395 bytes, checksum: 46b80b91909ac5f76eecbc9f4cb1f17f (MD5) Item released from any restrictions by Sarah Shreeves (sshreeve@illinois.edu) on 2012-06-29T10:00:14Z http://hdl.handle.net/2142/16534 en Copyright 2010 Min Xie synthetic methods azepanes azoniapropellane Synthesis of nitrogen-containing heterocycles using nitro compounds as building blocks: Part I: Synthesis of 3-substituted azepanes. Part II: Synthesis of 1-azoniapropellanes as phase transfer catalysts 2010-5 Chemistry 1413 Chemistry 0335 University of Illinois at Urbana-Champaign Dissertation Ph.D. PHD:Chemistry -UIUC 10KS0335PHD