| Full text | |
| Author(s): |
Vieira, Camila G.
[1, 2]
;
Angnes, Ricardo A.
[1]
;
Braga, Ataualpa A. C.
[1]
;
Gusevskaya, V, Elena
;
Rossi, Liane M.
[1]
Total Authors: 5
|
| Affiliation: | [1] Univ Sao Paulo, Inst Quim, BR-05508000 Sao Paulo, SP - Brazil
[2] Univ Fed Ouro Preto, Dept Quim, BR-35400000 Ouro Preto, MG - Brazil
Total Affiliations: 2
|
| Document type: | Journal article |
| Source: | MOLECULAR CATALYSIS; v. 517, JAN 2022. |
| Web of Science Citations: | 0 |
| Abstract | |
Fragrance substances derived from natural sources are essential to the fine chemical industry, being an interesting task to pursue. Herein, we present a smart catalytic oxidation route for bio-renewable (1R,5R)-sabinene obtainment in acetonitrile or acetone, just using Pd(OAc)2 as catalyst and hydrogen peroxide as an final oxidant. The products obtained from (1R,5R)-sabinene and their mixtures have a distinct and pleasant smell and therefore are candidates for fragrance and pharmacological applications. Three oxyfunctionalized products were obtained with ca. 80% combined selectivity at high substrate conversions. The major products, two novel isomeric caranetype ketones with a bicyclo{[}4.1.0] skeleton, were formed by expanding the five-membered ring in the sabinene molecule, while (-)-sabina ketone was produced as a minor product. An uncommon mechanistic route was suggested and supported by density functions theory (DFT), which could suitably explain the formation of these ketones. DFT results supported a proposed concerted mechanism for the C-C activation, like a semipinacol rearrangement, which includes a heterolysis of the Pd-C bond and synchronous cleavage of the C-C bond in an intermediate organopalladium peroxo complex. We highly believe that such findings allow a step forward a deep understanding of such organic transformation, helping in future new routes for value-added products. (AU) | |
| 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: | 19/02052-4 - Computational mechanistic studies of transition metal catalyzed functionalizations of alkenes: nonintuitive enantioselectivity induction modes applied on contiguos stereocenter formation and difunctionalizations. |
| Grantee: | Ricardo Almir Angnes |
| Support Opportunities: | Scholarships in Brazil - Post-Doctoral |
| FAPESP's process: | 14/25770-6 - New frontiers in cross-coupling reactions promoted by palladium: combining enantioselective catalysis, C-H activations, new materials and in flux reactions aiming at high efficiency and sustainability in synthetic processes |
| Grantee: | Carlos Roque Duarte Correia |
| Support Opportunities: | Research Projects - Thematic Grants |