Journal
ACS CATALYSIS
Volume 12, Issue 11, Pages 6495-6505Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.2c01391
Keywords
C-F bond cleavage; gem-difluorocyclopropane; allylic alkylation; PEPPSI catalyst; regioselectivity
Categories
Funding
- National Natural Science Foundation of China [22071266]
- Public Computing Cloud Platform at Renmin University of China
- Fundamental Research Funds for the Central Universities
- Renmin University of China [21XNLG04]
- Oberlin College
- Extreme Science and Engineering Discovery Environment [XSEDE TG-CHE210088]
- Oberlin College HPC cluster [NSF MRI 1427949]
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This study reports a catalytic method for controlling the selectivity of reactions, allowing access to diverse fluorinated 1,5-dienes from the same starting materials. Density functional theory calculations also revealed a ligand design for switching selectivity. This ligand-controlled approach is important for late-stage modification of complex molecules.
Controlling the selectivity of synthetically useful reactions has been a longstanding objective of organic chemistry. Wereport a regiodivergent synthetic protocol allowing access to diversefluorinated 1,5-dienes through Pd/NHC-catalyzed ring-openingallylation ofgem-difluorocyclopropanes. Density functional theory (DFT) calculations on regioselectivity-determining transitionstates provided critical insight into the design of the NHC ligand for switching regioselectivity. Consistent with the DFT predictions,N-heterocyclic carbene (NHC) ligands with bulkyorthosubstituents favored branched allylation, with the IHept ligand providing >20:1 branched/linear regioselectivity. NHC ligands with less hinderedorthosubstituents such as IMes favored thethermodynamically more stable linear products. We were able to carry out late-stage modification of various complex moleculesusing this protocol. Our ligand-controlled approach provides efficient access to regioisomericfluorinated 1,5-dienes from the samestarting materials and constitutes a valuable addition to the toolbox of diversity-oriented synthesis.
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