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IRON CARBONYL MEDIATED CYCLIZATIONS AND THEIR POTENTIAL APPLICATION IN SYNTHESIS

WANG, XIAOLONG
http://rave.ohiolink.edu/etdc/view?acc_num=case1095281934

Abstract Details

2004, Doctor of Philosophy, Case Western Reserve University, Chemistry.
Extension of the intramolecular coupling between a cyclohexadiene-Fe(CO)3 moiety and pendant olefins to make ä-lactam derivatives was investigated. ä-Lactams were found more difficult to form than ã-lactams, thus resulting in poorer yield and requiring longer reaction time. By introducing an ester group on the pendant olefin, increased yield was achieved. Intramolecular double cyclization between a cyclohexadiene-Fe(CO)3 complex and a pendant diene yielded a tricyclic molecule containing a spirocenter, with defined relative stereochemistry of four contiguous carbon centers. A convenient one-pot procedure to prepare angularly substituted bicyclic and tricyclic molecules with excellent diastereoselectivity in good yield was developed, by Fe(CO)5 promoted cyclization. Three transformations (complexation, isomerization and cyclization) were realized in a single operation. The product of this reaction might be a potential intermediate for synthesis of the alkaloid gelsemine. A new short protocol, rearrangement of the cyclohexadiene followed by cyclization, was discovered to give carbon spirocyclic molecules in fair to good yield. Diastereoselective cyclizations of diastereomeric amide complexes, which were prepared from chiral amines and racemic acid complexes, were investigated to show that the chirality, originating from the amine, can dictate the stereochemistry of the cyclization product by steric approach control. In one case, kinetic dynamic resolution during intramolecular coupling between the cyclohexadiene-Fe(CO)3 moiety and pendant olefin was demonstrated, which also showed an promise of a potential enantioselective methodology toward spriocyclic targets using racemic iron complexes.
Anthonyl Pearson (Advisor)
205 p.
Chemistry, Organic
1H; Hz; CYCLIZATIONS; CDCl3; 3Fe; NMR

Recommended Citations

Citations

  • WANG, X. (2004). IRON CARBONYL MEDIATED CYCLIZATIONS AND THEIR POTENTIAL APPLICATION IN SYNTHESIS [Doctoral dissertation, Case Western Reserve University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=case1095281934

    APA Style (7th edition)

  • WANG, XIAOLONG. IRON CARBONYL MEDIATED CYCLIZATIONS AND THEIR POTENTIAL APPLICATION IN SYNTHESIS. 2004. Case Western Reserve University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=case1095281934.

    MLA Style (8th edition)

  • WANG, XIAOLONG. "IRON CARBONYL MEDIATED CYCLIZATIONS AND THEIR POTENTIAL APPLICATION IN SYNTHESIS." Doctoral dissertation, Case Western Reserve University, 2004. http://rave.ohiolink.edu/etdc/view?acc_num=case1095281934

    Chicago Manual of Style (17th edition)

case1095281934
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© 2004, all rights reserved.
This open access ETD is published by Case Western Reserve University School of Graduate Studies and OhioLINK.