Banca de QUALIFICAÇÃO: PEDRO TENDRIH SODRÉ

Uma banca de QUALIFICAÇÃO de DOUTORADO foi cadastrada pelo programa.
STUDENT : PEDRO TENDRIH SODRÉ
DATE: 07/12/2022
TIME: 14:00
LOCAL: https://meet.google.com/jfy-ktzn-wvp
TITLE:

Investigationg intrinsic and environmental effects in chiral aldol catalysis by proline containing lipopeptides.

PAGES: 20
BIG AREA: Ciências Exatas e da Terra
AREA: Química
SUBÁREA: Físico-Química
SPECIALTY: Química Teórica
SUMMARY:

Abstract: Density Functional Theory (DFT) was used to investigate the aldol reaction used to generate C-C bonds between two carbonyl molecules. Recently, proline containing peptides with amide bonding were used as a catalytic phase in aqueous solution whose rich chemical environment results in high selectivity. The nudged Elastic Band (NEB) method was used to probe the stereo determining step considering two distinct mechanisms. Calculations uncovered a Houk-List like mechanism where the amide acts as a H-bond donor and another where the anionic additive trifluoracetic acid (TFA) acts as a proton relay. Both mechanisms resulted in low energy barriers of 4.49 and 3.76 kcal/mol respectively for the (SR) diastereomer, when starting from the lowest energy conformer. To investigate the catalytic effect of PRW/PRWG lipopeptide aggregate in water, molecular dynamics calculations were used to measure the propensity of the micellar phase to favor specific isomers. We observed that the micellar phase enhances encounters that favor the experimentally observed (SR / SS) isomers when compared to a pure cyclohexanone medium. 

BANKING MEMBERS:
Presidente - Interno ao Programa - 1544403 - MAURICIO DOMINGUES COUTINHO NETO
Membro Titular - Examinador(a) Interno ao Programa - 1544394 - PAULA HOMEM DE MELLO
Membro Titular - Examinador(a) Externo à Instituição - LUIS GUSTAVO DIAS - USP
Membro Suplente - Examinador(a) Externo ao Programa - 2218228 - LUANA SUCUPIRA PEDROZA