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Synthesis of Nitrogen-Containing Heterocycles via Carbenoid Insertion/Ring-Closing Metathesis Sequence

Pavlyuk, Oksana M.

Abstract Details

2011, Doctor of Philosophy (PhD), Ohio University, Chemistry and Biochemistry (Arts and Sciences).

A series of five- to nine-membered nitrogen-containing heterocycles were prepared via a general and efficient sequence featuring rhodium-catalyzed insertions of α-diazocarbonyls into the N-H or C-H bonds of a series of tert-butoxy-(Boc)-protected amines, followed by ring-closing metathesis catalyzed by ruthenium benzylidene complexes. The newly developed methodology allows easy and convenient access to highly functionalized azacycloalkenes in good yields and excellent selectivities.

Vinyl diazoacetoacetate and styryl diazoacetate were found to undergo exceptionally chemoselective carbenoid insertions into the N-H bonds of a series of Boc-protected amines in good yields; however, no stereoselectivity was observed for this process. In contrast, diastereo- and enantioselective C-H insertions and cyclopropanations were observed for the decomposition of styryl diazoacetate catalyzed by the same rhodium catalyst. Based on these findings, reactivity trends of rhodium carbenoids derived from styryl diazoacetate were postulated.

Mark McMills, Ph.D. (Advisor)
Stephen Bergmeier, Ph.D. (Committee Member)
Glen Jackson, Ph.D. (Committee Member)
Shawn Chen, Ph.D. (Committee Member)
198 p.

Recommended Citations

Citations

  • Pavlyuk, O. M. (2011). Synthesis of Nitrogen-Containing Heterocycles via Carbenoid Insertion/Ring-Closing Metathesis Sequence [Doctoral dissertation, Ohio University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=ohiou1303761092

    APA Style (7th edition)

  • Pavlyuk, Oksana. Synthesis of Nitrogen-Containing Heterocycles via Carbenoid Insertion/Ring-Closing Metathesis Sequence. 2011. Ohio University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=ohiou1303761092.

    MLA Style (8th edition)

  • Pavlyuk, Oksana. "Synthesis of Nitrogen-Containing Heterocycles via Carbenoid Insertion/Ring-Closing Metathesis Sequence." Doctoral dissertation, Ohio University, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=ohiou1303761092

    Chicago Manual of Style (17th edition)