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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

Intermolecular Noncovalent Hydroxy-Directed Enantioselective Heck Desymmetrization of Cyclopentenol: Computationally Driven Synthesis of Highly Functionalized cis-4-Arylcyclopentenol Scaffolds

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Silva, Juliana de Oliveira [1] ; Angnes, Ricardo A. [1] ; Menezes da Silva, Vitor H. [2] ; Servilha, Bruno M. [2] ; Adeel, Muhammad [3] ; Braga, Ataualpa A. C. [2] ; Aponick, Aaron [4] ; Correia, Carlos Roque D. [1]
Total Authors: 8
[1] Univ Estadual Campinas, Dept Quim Organ, BR-13083970 Campinas, SP - Brazil
[2] Univ Sao Paulo, Dept Quim Fundamental, Ave Lineu Prestes 748, Bl 05 Sup S1, 0552, Sao Paulo, SP - Brazil
[3] Gomal Univ, Dept Chem, Dera Ismail Khan 29050 - Pakistan
[4] Univ Florida, Dept Chem, Ctr Heterocycl Cpds, Gainesville, FL 32611 - USA
Total Affiliations: 4
Document type: Journal article
Source: Journal of Organic Chemistry; v. 81, n. 5, p. 2010-2018, MAR 4 2016.
Web of Science Citations: 25

New computationally driven protocols for the Heck desymmetrization of 3-cydopenten-1-ol with aryldiazonium tetrafluoroborates were developed. These new conditions furnished remarkable product selectivity originating from a resident hydroxyl group and the critical choice of the reaction solvent. Mechanistic insights gleaned from theoretical calculations of the putative transition states predicted toluene as an adequate solvent choice to attain high enantioselectivity by strengthening the noncovalent interaction of the substrate hydroxyl group and the chiral cationic palladium catalyst. Laboratory experiments validated the theoretical predictions, and by employing 2% MeOH/toluene as solvent, the Heck-Matsuda reaction provided exclusively the cis-4-arylcyclopentenols 3a-1 in good to excellent yields in enantiomeric excesses up to 99%. The performance of the new PyOx ligand (S)-4-tert-butyl-2-(3,5-dichloropyridin-2-yl)-4,5-dihydrooxazole was also successfully evaluated in the Heck-Matsuda desymmetrization of 3-cyclopenten-1-ol. The synthetic potential of these highly functionalized cis-4-arylcyclopentenols is illustrated by a gold-catalyzed synthesis of cyclopenta{[}b]benzofuran skeletons. (AU)

FAPESP's process: 13/04813-6 - Mechanistic studies of Heck-Matsuda reactions: a theoretical investigation
Grantee:Vitor Hugo Menezes da Silva
Support Opportunities: Scholarships in Brazil - Doctorate
FAPESP's process: 13/00544-0 - Substrate controlled Heck reactions using arenediazonium salts and the development of the enantioselective version of the Heck-Matsuda reaction.
Grantee:Juliana Manso de Oliveira Silva
Support Opportunities: Scholarships in Brazil - Post-Doctorate
FAPESP's process: 15/01491-3 - Theoretical study of cross-coupling reactions: homogeneous and heterogeneous catalysis
Grantee:Ataualpa Albert Carmo Braga
Support Opportunities: Regular Research Grants
FAPESP's process: 11/23832-6 - New methodological and mechanistic studies related to the Heck arylations employing arenediazonium salts and synthetic applications
Grantee:Carlos Roque Duarte Correia
Support Opportunities: Regular Research Grants
FAPESP's process: 13/07600-3 - CIBFar - Center for Innovation in Biodiversity and Drug Discovery
Grantee:Glaucius Oliva
Support Opportunities: Research Grants - Research, Innovation and Dissemination Centers - RIDC