The study of new guaianes, spiro and substituted benzenes derivatives from R-(-)-carvone and total synthesis in flow of spirodienal a and spirogien a methyl esther

• Grant number: 14/12001-4
• Support type: Scholarships in Brazil - Doctorate
• Effective date (Start): November 01, 2014
• Effective date (End): April 30, 2015
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Cooperation agreement: Coordination of Improvement of Higher Education Personnel (CAPES)
• Principal researcher: Timothy John Brocksom
• Grantee: Leandro de Carvalho Alves
• Home Institution: Centro de Ciências Exatas e de Tecnologia (CCET). Universidade Federal de São Carlos (UFSCAR). São Carlos , SP, Brazil

Abstract

In this research project we present a request for a six month PhD fellowship, presenting our results obtained so far and future studies for the publications of our results. This request arises from the fact that the student spent 1 year in England on a CNPq PhD sandwich programme, and when he came back to Brazil his original PhD fellowship had "disappeared". Some expected delays took place while conducting a second project in England, but very positive results were obtained and, in our opinion, support this request.In this request for a fellowship we describe our results on use of (R)-(-)-carvone as starting material for two synthetic routes leading to seven-membered ring compounds by ring expansion reactions. Stereoselective alkylations reactions (allylations and propargylations) of the cycloheptenone quiron were studied and the products were subjected to reactions with catalysts containing transition metals (Ru, Pd, Au). The objective here was the obtention of non-symmetrical spiro compounds, substituted benzenes and compounds containing an internal tris ketal group. Isopropenyl lithium addition at the cycloheptenone carbonyl group, and ring-closing metathesis reactions furnished guaiane type compounds.We performed a PhD sandwich for 12 months in the group of Professor Steven V. Ley at the Department of Chemistry, University of Cambridge, England. Part of the initial PhD project was developed in Cambridge along with activities related to a second project in collaboration with Professor Ley. Basically, the student had a valuable contact with Flow Chemistry, a relatively new technique from a methodological point of view. This experience was the fundamental objective of the sandwich, as Prof Ley is perhaps the leading world expert on flow chemistry. A clear demonstration of success is demonstrated by a participation in a publication in Angewandte Chemie (attached).Therefore, due our dedication to this second project, the original PhD project suffered serious delays. For this reason, we require 6 months of a doctoral fellowship, with the objective of completing the original projects, publication of these results and finishing up the PhD thesis (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)

ALVES, LEANDRO DE C.; DESIDERA, ANDRE L.; DE OLIVEIRA, KLEBER T.; NEWTON, SEAN; LEY, STEVEN V.; BROCKSOM, TIMOTHY J. A practical deca-gram scale ring expansion of (R)-(-)-carvone to (R)-(+)-3-methyl-6-isopropenyl-cyclohept-3-enone-1. ORGANIC & BIOMOLECULAR CHEMISTRY, v. 13, n. 28, p. 7633-7642, 2015. Web of Science Citations: 7.

BROCKSOM, TIMOTHY JOHN; DESIDERA, ANDRE LUIZ; ALVES, LEANDRO DE CARVALHO; DE OLIVEIRA, KLEBER THIAGO. The New Directions of Organic Synthesis. CURRENT ORGANIC SYNTHESIS, v. 12, n. 5, p. 496-522, 2015. Web of Science Citations: 6.