Intramolecular cyclization strategies for synthesizing medium-ring polycycles and the total synthesis of natural products

Donor-acceptor cyclopropanes;Indium catalysis;Formal homo-Nazarov reaction;Friedel-Crafts reaction;Intramolecular cyclizations;Tandem reactions;Alkylidene malonate monoamides

Patil, Dadasaheb V. ; France, Stefan Chemistry and Biochemistry Collard, David Kubanek, Julia Liotta, Charles Oyelere, Adegboyega ; France, Stefan

University:Georgia Institute of Technology

Department:Chemistry and Biochemistry

关键词: Donor-acceptor cyclopropanes;    Indium catalysis;    Formal homo-Nazarov reaction;    Friedel-Crafts reaction;    Intramolecular cyclizations;    Tandem reactions;    Alkylidene malonate monoamides;   

Others  :  https://smartech.gatech.edu/bitstream/1853/50118/1/patil_dadasaheb_v_201212_phd.pdf

美国|英语

来源: SMARTech Repository

【 摘 要 】

Carbo- and heterocyclic compounds are of great interest to chemists. Intramolecular cyclization strategies of donor-acceptor (D-A) cyclopropanes and alkylidene malonate monoamides have excellent potential for synthesis as they offer easy access to structurally-diverse compounds. The work described in this thesis accesses the scope of the In(OTf)3-catalyzed cyclization reaction of cyclopropanes and alkylidene malonate monoamides. In(OTf)3-catalyzed reactions of alkenyl and heteroaryl cyclopropyl ketones were examined in the synthesis of functionalized cyclohexenone-based derivatives (Chapter 2). Subsequent efforts to utilize a tandem cyclopropane ring-opening/Friedel-Crafts alkylation sequence of methyl 1-(1H-indolecarbonyl)-1-cyclopropanecarboxylates to prepare functionalized hydropyrido[1,2-a]indole-6(7H)-ones is discussed in Chapter 3. The extension of this tandem protocol towards the total synthesis of (±)-deethyleburnamonine is the subject of Chapter 6. Intramolecular Friedel-Crafts alkylation of N-indolyl alkylidene malonate monoamides was also examined. An In(OTf)3-catalyzed cyclization of substituted methyl 2-(1H-indole-1-carbonyl) acrylates afforded a series of 1H-pyrrolo[1,2-a]indole-3(2H)-ones (Chapter 4), whereas substrates with the indole 2-position blocked provided access to substituted 4H-pyrrolo[3,2,1-ij]quinolin-4-ones (Chapter 5).