Regio- and diastereoselective Pd-catalyzed aminochlorocyclization of allylic carbamates: scope, derivatization, and mechanism.
| Title: | Regio- and diastereoselective Pd-catalyzed aminochlorocyclization of allylic carbamates: scope, derivatization, and mechanism. |
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| Authors: | Papa Spadafora B; Department of Chemistry, Federal University of Sao Paulo, UNIFESP. Prof. Artur Riedel Street 275, lab 10, 09972-270, Diadema, SP, Brazil. alessandro.rodrigues@unifesp.br.; Moreira Ribeiro FW; Department of Fundamental Chemistry, Institute of Chemistry, University of Sao Paulo, Av. Prof. Lineu Prestes, 748, 05508-000, Sao Paulo, SP, Brazil and Department of Chemistry, University of Victoria, P. O. Box 3065, Victoria, BC V8W 3V6, Canada.; Matsushima JE; Department of Chemistry, Federal University of Sao Paulo, UNIFESP. Prof. Artur Riedel Street 275, lab 10, 09972-270, Diadema, SP, Brazil. alessandro.rodrigues@unifesp.br.; Ariga EM; Department of Chemistry, Federal University of Sao Paulo, UNIFESP. Prof. Artur Riedel Street 275, lab 10, 09972-270, Diadema, SP, Brazil. alessandro.rodrigues@unifesp.br.; Omari I; Department of Chemistry, University of Victoria, P. O. Box 3065, Victoria, BC V8W 3V6, Canada.; Soares PMA; Department of Chemistry, Federal University of Sao Paulo, UNIFESP. Prof. Artur Riedel Street 275, lab 10, 09972-270, Diadema, SP, Brazil. alessandro.rodrigues@unifesp.br.; de Oliveira-Silva D; Department of Chemistry, Federal University of Sao Paulo, UNIFESP. Prof. Artur Riedel Street 275, lab 10, 09972-270, Diadema, SP, Brazil. alessandro.rodrigues@unifesp.br.; Vinhato E; Department of Chemistry, Federal University of Sao Paulo, UNIFESP. Prof. Artur Riedel Street 275, lab 10, 09972-270, Diadema, SP, Brazil. alessandro.rodrigues@unifesp.br.; McIndoe JS; Department of Chemistry, University of Victoria, P. O. Box 3065, Victoria, BC V8W 3V6, Canada.; Carita Correra T; Department of Fundamental Chemistry, Institute of Chemistry, University of Sao Paulo, Av. Prof. Lineu Prestes, 748, 05508-000, Sao Paulo, SP, Brazil.; Rodrigues A; Department of Chemistry, Federal University of Sao Paulo, UNIFESP. Prof. Artur Riedel Street 275, lab 10, 09972-270, Diadema, SP, Brazil. alessandro.rodrigues@unifesp.br. |
| Source: | Organic & biomolecular chemistry [Org Biomol Chem] 2021 Jun 30; Vol. 19 (25), pp. 5595-5606. |
| Publication Type: | Journal Article; Research Support, Non-U.S. Gov't |
| Language: | English |
| Journal Info: | Publisher: Royal Society of Chemistry Country of Publication: England NLM ID: 101154995 Publication Model: Print Cited Medium: Internet ISSN: 1477-0539 (Electronic) Linking ISSN: 14770520 NLM ISO Abbreviation: Org Biomol Chem Subsets: MEDLINE; PubMed not MEDLINE |
| Imprint Name(s): | Original Publication: Cambridge, UK : Royal Society of Chemistry, c2003- |
| 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. |
| Entry Date(s): | Date Created: 20210607 Date Completed: 20220308 Latest Revision: 20220308 |
| Update Code: | 20260130 |
| DOI: | 10.1039/d1ob00670c |
| PMID: | 34096563 |
| Database: | MEDLINE |
Journal Article; Research Support, Non-U.S. Gov't