Hypervalent iodine in the synthesis of cyclic compounds: development of reactions and total synthesis of natural products

• Grant number: 12/10568-1
• Support Opportunities: Regular Research Grants
• Duration: November 01, 2012 - October 31, 2014
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Luiz Fernando da Silva Júnior
• Grantee: Luiz Fernando da Silva Júnior
• Host Institution: Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil

Abstract

Cyclic compounds are an important moiety in most of the natural products. Moreover, all top selling drugs that are small organic molecules possess at least one ring in its structure.. In this project we plan to synthesize several kinds of cyclic compounds using as tool iodine, either in the form of the classic moleculas iodine or in the modern version of the hypervalent iodine compounds. This project is divided in two big parts. The first is divided in seven projects: i) ring contraction reaction; ii) ring expansion reactions; iii) ciclofunctionalization; iv) C-H activation through benzylic oxidation; v) investigation of the properties in synthetic organic chemistry of new halogens-cucurbit[6]uril complexes; vi) introduction of an alkynyl group at a-carbon of aldehydes; vii) preparation and reactivity of new quiral iodine(III) compounds in ring contractions, in a-oxy-tosylation and spirolactonization. Most of these reaction will be investigated in the context of the total synthesis of natural products, which is the subject of part 2 of this project. We present proposals for the asymmetric synthesis of molecules isolated recently, which have challenging structural aspects, such as raputindole A, raputindole D, and argutanes. We will also study a short route toward (+)-cis-trikentrin A and a sesquiterpenene. Many of the molecules herein obtained will submitted to biological studies: a) anti-tumor in the group of Prof. J. E. Carvalho, UNICAMP; b) malaria in the group of Prof. Alejandro Miguel Katzin, ICB-USP; c) Leishmaniasis in the group of Prof. Marcelo Dias Baruffi, FCFRP-USP. (AU)

Scientific publications

(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)

LEMOS SILVA, SIGUARA BASTOS; DELLA TORRE, ADRIANA; DE CARVALHO, JOAO ERNESTO; TASCA GOIS RUIZ, ANA LUCIA; SILVA, JR., LUIZ F.. Seven-Membered Rings through Metal-Free Rearrangement Mediated by Hypervalent Iodine. Molecules, v. 20, n. 1, p. 1475-1494, JAN 2015. (12/10568-1, 10/16042-6)