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 Opportunities: Scholarships in Brazil - Doctorate
• Start date: March 01, 2013
• End date: February 28, 2017
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Antonio Carlos Bender Burtoloso
• Grantee: Barbara Bernardim de Souza
• Host 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)

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. (13/18009-4, 12/22274-2, 13/25504-1)

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. (13/50312-9, 13/18009-4, 12/22274-2, 13/25504-1)

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. (12/22274-2, 13/25504-1)

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. (12/22274-2, 09/54040-8, 12/04685-5)

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. (12/22274-2, 13/25504-1)

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; et al. Stoichiometric and irreversible cysteine-selective protein modification using carbonylacrylic reagents. NATURE COMMUNICATIONS, v. 7, OCT 26 2016. (15/07509-1, 13/25504-1, 12/22274-2)

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 (IQSC/BT) São Carlos.