Regioselective Functionalization of Ester-, Amide-, Carbonate-, and Carbamate-Substituted 2-Phenyl-2-oxazolines with Mixed Lithium-Magnesium Amides

Author(s)

Bozzini, Leandro A. ^[1] ; dos Santos, Thiago ^[1] ; Murie, Valter E. ^[1] ; de Mello, Murilo B. M. ^[1] ; Vessecchi, Ricardo ^[2] ; Clososki, Giuliano C. ^[1]

Affiliation

^[1] Univ Sao Paulo, Fac Ciencias Farmaceut Ribeirao Preto, Dept Ciencias BioMol, Av Do Cafe S-N, BR-14040903 Ribeirao Preto, SP - Brazil

^[2] Univ Sao Paulo, Fac Filosofia Ciencias & Letras Ribeirao Preto, Dept Quim, BR-14090901 Ribeirao Preto, SP - Brazil

• Document type: Journal article
• Source: Journal of Organic Chemistry; v. 86, n. 1, p. 1204-1215, JAN 1 2021.
• Web of Science Citations: 0

Abstract

We have prepared novel highly functionalized benzene derivatives by regioselective metalation of ester-, amide-, carbamate-, and carbonate-substituted 2-phenyl-2-oxazolines with mixed lithium-magnesium amides followed by reaction with different electrophiles. While a complementary metalation site can be accessed by using different bases, steric and electronic effects promoted by the aromatic ring substituents also play an important role in reaction regioselectivity. Computational calculations of the aromatic hydrogen pK(a) values have helped us to rationalize the metalation preference by the complex-induced proximity effect concept. (AU)

• FAPESP's process: 18/14150-8 - Selective aromatic functionalization: Methodological Studies and new applications in the synthesis of BIOATIVE compounds
• Grantee: Giuliano Cesar Clososki
• Support Opportunities: Regular Research Grants
• FAPESP's process: 15/21364-6 - Applicantion of Organometallic Reagents in the Directed Functionalization of Quinolines Aimming the Synthesis of Medicinal Interest Compounds
• Grantee: Valter Eduardo Murie
• Support Opportunities: Scholarships in Brazil - Doctorate
• FAPESP's process: 14/23604-1 - Computational chemistry: a tool to studies of mass spectrometry, reactivity and fragmentation/reaction mechanisms of organic compounds
• Grantee: Ricardo Vessecchi Lourenço
• Support Opportunities: Regular Research Grants