Hypervalent iodine: methodology and total synthesis

• Grant number: 15/00527-4
• Support Opportunities: Regular Research Grants
• Duration: August 01, 2015 - July 31, 2017
• 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

Our research group started to investigate reactions promoted by hypervalent iodine in 2005. Initially, only ring contractions were studied. However, other transformations, such as, electrophilic cyclizations and alkynylations were gradually incorporated into the group repertory. Many challenges still remain and this projects aims to develop further reaction mediated by hypervalent iodine, including applications in total synthesis. Our specific goals in methodology are: a) investigate the ring contraction reaction in the synthesis of heterocycles and tetralines, including an asymmetric version using chiral iodine(III); b) develop a method to obtain indanes substituted in the position 2 through ring contraction reaction. We plan to apply this reaction in the synthesis of donepezil; c) the synthesis of heterocycles will be studied through electrophilic cyclization promoted by iodine/iodine(III), which can lead to products different than those obtained under traditional conditions; d) introduction of triple bonds in diverse compounds will be performed using hypervalent iodine in the formation of a C-C bond, to increase the scope of the recent and excellent results of our group. Regarding total syntheses, we plan the asymmetric total synthesis of raputindole A, raputindole D, argutanes and populene D and the racemic synthesis of a sesquiterpene. The synthesis of these molecules was not reported up to now. We will reactions developed in our group in these routes. Antiproliferative activity will be evaluated for natural products and compounds with a privileged scaffold. (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)

TEODORO, BRUNO V. M.; SILVA, JR., LUIZ F.. Metal-Free Synthesis of Homopropargylic Alcohols from Aldehydes. Journal of Organic Chemistry, v. 82, n. 22, p. 11787-11791, NOV 17 2017. (15/00527-4)

TEODORO, BRUNO V. M.; SILVA, JR., LUIZ F.. Sequential Michael Addition/Electrophilic Alkynylation: Synthesis of alpha-Alkynyl-beta-Substituted Ketones and Chromanones. Journal of Organic Chemistry, v. 83, n. 21, p. 13604-13611, NOV 2 2018. (15/00527-4)