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Stereocontrolled functionalization of dienes using organoiron chemistry

Chang, Kieyoung

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1994, Doctor of Philosophy, Case Western Reserve University, Chemistry.
Conversion of η4-cycloheptatriene-Fe(CO)2P(OPh)3 (2.23) to cycloheptadienone-Fe(CO)2P(Ph)3 (2.25) was accomplished by hydroboration/oxidation followed by Swern oxidation. Methylation and hydroxylation of the enolate from 2.25 proceeds with complete stereoselectivity, anti to the metal moiety, and introduction of two methyl or hydroxyl groups at the α and α′ positions was accomplished in high overall yield. Reduction of dialkylated ketone 2.30 occurs with high stereoselectivity and is controlled by the boat conformation adopted by this coplex. The stereochemistry of the corresponding protected alcohol complex 2.34 was confirmed by single crystal X-ray structure determination. Demetallation of this complex, followed by stereocontrolled oxygenation and Mitsunobu reaction, then ring cleavage provides methodology for the construction of a C(9)-C(14) subunit of calyculin A. Stereoselective cuprate addition to the enone 2.85, syn to the methoxymethyl ether group, gives the cycloheptanone derivative 2.86 Hydroxylation of an enolsilane obtained from the cuprate adduct on 2.85, followed by reduction and ring cleavage, provides methodology for the construction of a C(19)-C(25) subunit of swinholide A. Asymmetric complexation of dienoic acid amides, derived from chiral amines, were st udied. Syntheses of dienoic acid amides proceed by the reaction of dienoic acid with chiral secondary amines such as Evans' oxazolidinone, (-)-(2R,5R)-dimethylpyrrolidine, or (S)-(-)-α , α-diphenyl-2-pyrrolidinemethanol. Complexation of the dienoic acid amide 4.34 occurs with complete stereoselectivity, anti to the substituent, to give the complex 4.41 in optically pure form. The stereochemistry of the complex 4.41 was determined by single crystal X-ray structure determination. ftn*Please refer to dissertation for diagrams
Anthony Pearson (Advisor)
237 p.

Recommended Citations

Citations

  • Chang, K. (1994). Stereocontrolled functionalization of dienes using organoiron chemistry [Doctoral dissertation, Case Western Reserve University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=case1061302276

    APA Style (7th edition)

  • Chang, Kieyoung. Stereocontrolled functionalization of dienes using organoiron chemistry. 1994. Case Western Reserve University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=case1061302276.

    MLA Style (8th edition)

  • Chang, Kieyoung. "Stereocontrolled functionalization of dienes using organoiron chemistry." Doctoral dissertation, Case Western Reserve University, 1994. http://rave.ohiolink.edu/etdc/view?acc_num=case1061302276

    Chicago Manual of Style (17th edition)