| Full text | |
| Author(s): |
Fontana, Liniquer A.
[1]
;
Almeida, Marlon P.
[1]
;
Alcantara, Arthur F. P.
[1, 2]
;
Rigolin, Vitor H.
[1]
;
Ribeiro, Marcos A.
[3]
;
Barros, Wdeson P.
[1]
;
Megiatto, Jackson D.
[1]
Total Authors: 7
|
| Affiliation: | [1] Univ Campinas UNICAMP, Inst Chem, POB 6154, BR-13083970 Campinas, SP - Brazil
[2] Inst Fed Sertao Pernambucano, Estr Tamboril, BR-56200000 Ouricuri - Brazil
[3] Univ Fed Espirito Santo, Dept Quim, Av Fernando Ferrari 514, BR-29075910 Vitoria, ES - Brazil
Total Affiliations: 3
|
| Document type: | Journal article |
| Source: | NATURE COMMUNICATIONS; v. 11, n. 1 DEC 11 2020. |
| Web of Science Citations: | 3 |
| Abstract | |
Selectivity in N-H and S-H carbene insertion reactions promoted by Ru(II)porphyrinates currently requires slow addition of the diazo precursor and large excess of the primary amine and thiol substrates in the reaction medium. Such conditions are necessary to avoid the undesirable carbene coupling and/or multiple carbene insertions. Here, the authors demonstrate that the synergy between the steric shielding provided by a Ru(II)porphyrinate-based macrocycle with a relatively small central cavity and the kinetic stabilization of otherwise labile coordinative bonds, warranted by formation of the mechanical bond, enables single carbene insertions to occur with quantitative efficiency and perfect selectivity even in the presence of a large excess of the diazo precursor and stoichiometric amounts of the primary amine and thiol substrates. As the Ru(II)porphyrinate-based macrocycle bears a confining nanospace and alters the product distribution of the carbene insertion reactions when compared to that of its acyclic version, the former therefore functions as a nanoreactor. Selectivity in carbene insertion reactions promoted by Ru(II)porphyrinates is achieved only upon careful control of substrate stoichiometry. Here, the authors demonstrate that endotopic catalysis and formation of mechanical bonds enables carbene insertions to occur selectively and in quantitative yield regardless of substrate stoichiometry. (AU) | |
| FAPESP's process: | 17/06752-5 - Development of New Template Strategies for the Synthesis of Polyrotaxanes |
| Grantee: | Liniquer André Fontana |
| Support Opportunities: | Scholarships in Brazil - Doctorate |
| FAPESP's process: | 13/22160-0 - Development of original synthetic strategies for the preparation of supramolecular Interlocked polymers |
| Grantee: | Jackson Dirceu Megiatto Junior |
| Support Opportunities: | Research Grants - Young Investigators Grants |
| FAPESP's process: | 15/23761-2 - Development of new well-defined multifunctional dendrimers for applications in nanomedicine |
| Grantee: | Cátia Cristina Capêlo Ornelas Megiatto |
| Support Opportunities: | Regular Research Grants |