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Study in the photochemical Wolff rearrangement from a,b-unsaturated diazoketones. aplication in diversity synthesis of nitrogen and oxygen heterocycles

Grant number: 12/22274-2
Support type:Scholarships in Brazil - Doctorate
Effective date (Start): March 01, 2013
Effective date (End): February 28, 2017
Field of knowledge:Physical Sciences and Mathematics - Chemistry
Principal Investigator:Antonio Carlos Bender Burtoloso
Grantee:Barbara Bernardim de Souza
Home Institution: Instituto de Química de São Carlos (IQSC). Universidade de São Paulo (USP). São Carlos , SP, Brazil
Associated scholarship(s):15/07509-1 - Site-specific modification of proteins via aqueous Horner-Wadsworth-Emmons reaction followed by Wolff rearrangement, BE.EP.DR

Abstract

This research project aims to study and increase the range of applications of a,b-unsaturated diazoketones. Considered as potential bifunctional intermediates, these compounds can be used in the quick and efficient synthesis of many molecules of interest, as already demonstrated by Burtoloso et al. In this regard, it will be assessed in detail the Wolff rearrangement in the presence of new nucleophiles, for the synthesis of new alkaloids and new classes of molecules. At first we will evaluate the preparation of novel polyhydroxylated alkaloids using the methodology already described by Burtoloso, as well as establish collaborations for the biological evaluation of these compounds against glycosidases. Secondly, the study of the Wolff rearrangement from unsaturated diazoketones in the presence of various amines and subsequent application in the total synthesis of the compound JP4-039 and analogs will be tested. Lastly, the realization of the Wolff rearrangement with unsaturated diazoketones in the presence of vinyl and allyl alcohols (with the intention to study [2 +2] and [4 +2] intramolecular cycloaddition reactions) may provide a new methodology for the synthesis of cyclobutanes and cyclohexanes in few steps.

Scientific publications (6)
(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)
BERNARDIM, BARBARA; CAL, PEDRO M. S. D.; MATOS, MARIA J.; OLIVEIRA, BRUNO L.; MARTINEZ-SAEZ, NURIA; ALBUQUERQUE, INES S.; PERKINS, ELIZABETH; CORZANA, FRANCISCO; BURTOLOSO, ANTONIO C. B.; JIMENEZ-OSES, GONZALO; BERNARDES, GONCALO J. L. Stoichiometric and irreversible cysteine-selective protein modification using carbonylacrylic reagents. NATURE COMMUNICATIONS, v. 7, OCT 26 2016. Web of Science Citations: 43.
BERNARDIM, BARBARA; COUCH, ERICA D.; HARDMAN-BALDWIN, ANDREA M.; BURTOLOSO, ANTONIO C. B.; MATTSON, ANITA E. Divergent Roles of Urea and Phosphoric Acid Derived Catalysts in Reactions of Diazo Compounds. SYNTHESIS-STUTTGART, v. 48, n. 5, p. 677-686, MAR 2016. Web of Science Citations: 12.
BURTOLOSO, ANTONIO C. B.; DIAS, RAFAEL M. P.; BERNARDIM, BARBARA. alpha,beta-Unsaturated Diazoketones as Useful Platforms in the Synthesis of Nitrogen Heterocycles. ACCOUNTS OF CHEMICAL RESEARCH, v. 48, n. 4, p. 921-934, APR 2015. Web of Science Citations: 36.
BERNARDIM, BARBARA; HARDMAN-BALDWIN, ANDREA M.; BURTOLOSO, ANTONIO C. B. LED lighting as a simple, inexpensive, and sustainable alternative for Wolff rearrangements. RSC ADVANCES, v. 5, n. 18, p. 13311-13314, 2015. Web of Science Citations: 16.
BURTOLOSO, ANTONIO C. B.; SANTIAGO, JOAO V.; BERNARDIM, BARBARA; TALERO, ALEXANDER G. Advances in the Enantioselective Metal-catalyzed N-H and O-H Insertion Reactions with Diazocarbonyl Compounds. CURRENT ORGANIC SYNTHESIS, v. 12, n. 5, p. 650-659, 2015. Web of Science Citations: 8.
BERNARDIM, BARBARA; BURTOLOSO, ANTONIO C. B. A two-step synthesis of the bioprotective agent JP4-039 from N-Boc-L-leucinal. Tetrahedron, v. 70, n. 20, p. 3291-3296, MAY 20 2014. Web of Science Citations: 6.
Academic Publications
(References retrieved automatically from State of São Paulo Research Institutions)
SOUZA, Barbara Bernardim de. New methodologies in organic synthesis using the Wolff rearrangement from unsaturated diazoketones. 2017. Doctoral Thesis - Universidade de São Paulo (USP). Instituto de Química de São Carlos São Carlos.

Please report errors in scientific publications list by writing to: cdi@fapesp.br.