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  • Stereospecific Synthesis of Stereotriad Motifs and Alkenes Using Enantioenriched sp³-Hybridized Carbenoids

    Creator:
    Xun, Sun
    Abstract:
    Enantioenriched sp³-hybridized carbenoid reagents CR1R2MX (X = nucleofuge, M = electrofuge) of different types were investigated for the synthesis of polysubstituted alkyl chains by iterative stereospecific reagent-controlled homologation (StReCH) and for the stereospecific connective synthesis of alkenes by eliminative cross-coupling. In the first part, putative enantioenriched α-chloroalkyllithiums (CHRLiCl) were employed...
    Resource Type:
    Dissertation
    Full Text:
    -yl)ethyllithium. The (R)- or (S)-configured chloroalkyllithium reagents were generated by sulfoxide

  • Analysis of the mechanism of sulfoxide-lithium exchange and the reactive intermediate in stereospecific reagent-controlled homologation (StReCH)

    Creator:
    Hoyt, Amanda
    Abstract:
    The stereospecific reagent-controlled homologation (StReCH) of boronic esters with enantioenriched carbenoid species generated in situ by the addition of organolithium initiators to stereodefined α-chloroalkyl aryl sulfoxides was previously reported. The reaction of an organolithium with an α-chloroalkyl aryl sulfoxide ostensibly generates an α-chloroalkyllithium via sulfoxide-lithium exchange; however, the true nature...
    Resource Type:
    Masters Thesis
    Full Text:
    ), 2.73 (3H, s) ppm; 13C NMR (700 MHz, CDCl3)  31 145.9 (0), 131.2 (1), 129.6 (2C, 1), 123.8 (2C

  • Scaffold reactivity and large scale Synthesis of organocatalyzed Yamada-Otani Condensation product and investigation of the synthesis and properties of axially chiral 8,8'-biquinolyls and 8-(naphtha-1-yl)quinolines

    Creator:
    Banerjee, Somdev
    Abstract:
    In Part I, (4S,5R)-4,5-dimethyl-4-phenylcyclohex-2-enone (19a) was prepared in 73% yield with high enantio- and diastereo-selectivity (er > 98:2, dr > 20:1) on a multigram scale by a Yamada-Otani condensation between (E)-pent-3-en-2-one and 2-phenylpropanal catalyzed by a sulfonimide derivative of (S)-proline (18, HuaCat®). Synthetically useful transformations of the cyclohexenone product 19a...
    Resource Type:
    Dissertation
    Full Text:
    - phenylpropanal catalyzed by a sulfonimide derivative of (S)-proline (18, HuaCat®). Synthetically useful

  • Stereocontrolled Synthesis of Allenes by Eliminative Cross-Coupling of Carbenoids

    Creator:
    Cao, Yang
    Abstract:
    The bimolecular reaction of two carbenoid species resulting in the formation of a carbon-carbon double bond (pi-system), referred to herein as carbenoid eliminative cross-coupling (CEXC), involves a series of three fundamental steps: (i) ate-complex formation (transmetalation), (ii) 1,2-metalate rearrangement, and (iii) beta-elimination. All three steps are stereospecific and so the...
    Resource Type:
    Dissertation
    Full Text:
    stereochemical configuration, (R) or (S)] with an sp2-hybridized alkylidene-type carbenoid [with defined

  • Atropisomeric 8,8'-biquinolyl derivatives : synthesis, properties and applications

    Creator:
    Milicevic, Selena D.
    Abstract:
    7,7'-Dihydroxy-8,8'-biquinolyl (azaBINOL) was prepared from 7-hydroxyquinoline via N,N-dimethyl O-quinol-7-yl carbamate by directed ortho-metallation followed by FeCl₃-mediated oxidative coupling of the 8-lithioquinoline intermediate. Saponification of the resulting dicarbamate provided crystalline (±)-azaBINOL in 56% overall yield. 6,6'-Bis(dimethylaminocarbonyl)-7,7'-dihydroxy-8,8´-biquinolyl was prepared from the same dicarbamate by a double anionic-Fries rearrangement in 43% yield. 7,7'-Bis(diethylamino-carbonyloxy)-6,6'-diiodo-8,8´-biquinolyl...
    Resource Type:
    Dissertation
    Full Text:
    ΔS‡ = 18.7 cal mol–1 K–1 by Eyring plot analysis. The further functionalized 2,2´-di-tert-butyl

  • Part I: Synthesis and evaluation of synosutine as an inhibitor of serotonin, norepinephrine, and dopamine transporters Part II: Asymmetric approach to the tetracyclic core of neomangicol A

    Creator:
    Juniku, Rajan B.
    Abstract:
    Part I: Racemic and asymmetric syntheses of a new substance with prospective antidepressant properties were achieved. In vitro assays with synthetic racemates (±)-25 and (±)-26 suggested that the former is a relatively selective inhibitor of serotonin transporter whereas the latter is a more balanced inhibitor of both serotonin and norepinephrine...
    Resource Type:
    Dissertation
    Full Text:
    accomplished from the monoterpene (S)-(+)-carvone via radical cyclization and a series of Baeyer-Villiger

  • Stereoselective synthesis & application of enantioenriched main group α-haloalkyl organometal reagents

    Creator:
    Emerson, Christopher R.
    Abstract:
    Sulfoxide-ligand exchange (SLE) and asymmetric halogen-metal exchange (AHME) processes were separately examined for the enantioselective synthesis of functionalized alpha-haloalkylmetal (carbenoid) reagents. Carbenoids derived from SLE were used to effect stereospecific reagent-controlled homologation (StReCH) of boronic esters and those generated via AHME were engaged in Darzens-type chemistry with aldehydes. Abstract for...
    Resource Type:
    Dissertation
    Full Text:
    boronate with two separate portions of (S)-1-[2H]-1-chloro-2-(1,3-dioxolan-2-yl)ethyllithium (generated

  • Graphite intercalation compounds containing fluoroanions

    Creator:
    Katinonkul, Watcharee
    Abstract:
    New chemical synthesis strategies have been investigated for the preparation of acceptor-type graphite intercalation compounds (GIC's) with fluoroanions in order to obtain new materials and to develop a better understanding of the synthetic approaches and properties of the products. New GIC's containing borate chelate anion such as bis(oxalato)borate, CxB[OC(O)C(O)O]₂•δF, are...
    Resource Type:
    Dissertation
    Full Text:
    (perfluoropinacolato)borate, CxB[OC(CF3)2C(CF3)2O]2·δF, and bis(hexafluorohydroxyisobutyrato)borate, CxB[OC(CF3)2C

  • Studies toward the synthesis of halichlorine and pinnaic acid

    Creator:
    Korf, Eric A.
    Abstract:
    Three approaches toward the core of halichlorine and pinnaic acid are described. The first approach entails a racemic transannular nitrone-olefin [3+2] cycloaddition from nitrone 238. Construction of the nitrone 238 began with aldehyde 241. Another key feature in this route involved a ring-closing metathesis for the formation of a 14-membered...
    Resource Type:
    Dissertation
    Full Text:
    debenzylation and desilylations ended with global acetyl protection to form 4. The two 4’s were analyzed by

  • Aryl acetylene substituent effects : the synthesis and application of biaryls

    Creator:
    Naffziger, Michael R.
    Abstract:
    The work described herein details the synthesis and application of biphenyls that probe the effects of hydrogen, Cl / Br, and methyl substituents on the aryl ring of the terminal acetylenic carbon. From this work, we successfully developed the rapid synthesis of phenyl acetylenes in 3-4 steps from inexpensive commercially...
    Resource Type:
    Masters Thesis
    Full Text:
    , O.; Tasler, S. Prog. Chem. Org. Nat. Prod. 2001, 82, 1-293. 2 (a) McCarthy, M.; Guiry, P. J