Regio- and diastereoselective Pd-catalyzed aminochlorocyclization of allylic carbamates: scope, derivatization, and mechanism

Author(s):Show less -

Papa Spadafora, Bruna ^[1] ; Moreira Ribeiro, Francisco Wanderson ^{[2, 3]} ; Matsushima, Jullyane Emi ^[1] ; Ariga, Elaine Miho ^[1] ; Omari, Isaac ^[2] ; Soares, Priscila Machado Arruda ^[1] ; de Oliveira-Silva, Diogo ^[1] ; Vinhato, Elisangela ^[1] ; McIndoe, J. Scott ^[2] ; Carita Correra, Thiago ; Rodrigues, Alessandro ^[1]

Affiliation

^[1] Univ Fed Sao Paulo, Dept Chem, UNIFESP Prof Artur Riedel St 275, Lab 10, BR-09972270 Diadema, SP - Brazil

^[2] Univ Victoria, Dept Chem, POB 3065, Victoria, BC V8W 3V6 - Canada

^[3] Univ Sao Paulo, Inst Chem, Dept Fundamental Chem, Av Prof Lineu Prestes 748, BR-05508000 Sao Paulo, SP - Brazil

• Document type: Journal article
• Source: ORGANIC & BIOMOLECULAR CHEMISTRY; v. 19, n. 25 JUN 2021.
• Web of Science Citations: 0

Abstract

The regio- and diastereoselective synthesis of oxazolidinones via a Pd-catalyzed vicinal C-N/C-Cl bond-forming reaction from internal alkenes of allylic carbamates is reported. The oxazolidinones are obtained in yields of 44 to 95% with high to excellent diastereoselectivities (from 6 : 1 to >20 : 1 dr) from readily available precursors. This process is scalable, and the products are suitable for the synthesis of useful amino alcohols. A detailed theoretical and experimental mechanistic study was carried out to describe that the reaction proceeds through an anti-aminopalladation of the alkene followed by an oxidative C-Pd(ii) cleavage with retention of the carbon stereochemistry to yield the major diastereomer. The role of Cu(ii) in a C-Cl bond-forming mechanism step has also been proposed. (AU)

• FAPESP's process: 19/16026-5 - Cyclization reactions promoted by Pd/Cu Catalysts
• Grantee: Francisco Wanderson Moreira Ribeiro
• Support Opportunities: Scholarships abroad - Research Internship - Doctorate
• FAPESP's process: 16/21676-0 - Enantioselective haloamination reactions aiming the synthesis of aminodiols
• Grantee: Alessandro Rodrigues
• Support Opportunities: Regular Research Grants
• FAPESP's process: 15/08539-1 - Multi-User Equipment approved in grant 2014/15962-5: ion trap mass spectrometer modified to perform infrared vibrational spectroscopy (IRMPD)
• Grantee: Thiago Carita Correra
• Support Opportunities: Multi-user Equipment Program
• FAPESP's process: 16/17328-7 - Enantioselective haloamination reactions aiming aminodiols synthesis
• Grantee: Bruna Papa Spadafora
• Support Opportunities: Scholarships in Brazil - Master
• FAPESP's process: 17/18485-1 - Mechanistic studies of haloamination reactions promoted by metallic and organic catalysts
• Grantee: Francisco Wanderson Moreira Ribeiro
• Support Opportunities: Scholarships in Brazil - Doctorate
• FAPESP's process: 14/15962-5 - Reaction mechanism of asymmetric catalysts by mass spectrometry and gas-phase vibrational ion spectroscopy
• Grantee: Thiago Carita Correra
• Support Opportunities: Research Grants - Young Investigators Grants
• FAPESP's process: 19/25634-9 - Real-time reaction analysis in complex matrices by advanced mass spectrometry techniques
• Grantee: Thiago Carita Correra
• Support Opportunities: Regular Research Grants