85630-37-1

Upstream product

• 65009-00-9 O-phenyl N,N-diethylcarbamate 
• 88-10-8 N,N-diethylcarbamyl chloride 
• 108-95-2 phenol 
• 13170-43-9 (trimethylsilyl)methylmagnesium chloride 
• 101270-37-5 O-(2-N,N-diethylcarbamoyloxy)phenyl N,N-diethylcarbamate 
• 75-77-4 chloro-trimethyl-silane 
• 85630-35-9 N,N-diethyl-2-methylcarbamoyloxybenzene 

Downstream Products

• 182962-47-6 N,N-diethyl-2-(2-hydroxy)phenyl acetamide 

Relevant academic research and scientific papers

Directed ortho-Metalation of O-Aryl N,N-Dialkylcarbamates: Methodology, Anionic ortho-Fries Rearrangement, and Lateral Metalation

The directed ortho-lithiation reactions of O-aryl N,N-dialkylcarbamates as well as O-1-naphthyl and O-2-naphthyl N,N-dialkylcarbamates with sec-butyllithium/tetramethylethylenediamine (sBuLi/TMEDA) followed by quenching with various electrophiles afford a range of polysubstituted aromatic compounds. If the solutions of the ortho-lithiated carbamates are warmed to room temperature without the addition of external electrophiles, salicylamide and 1- and 2-hydroxynaphthamide derivatives are formed through anionic ortho-Fries rearrangements. The relative stabilities and reactivities of different O-aryl N,N-dialkylcarbamates were investigated. The lateral metalation of 2-tolyl carbamates with lithium diisopropylamide (LDA) provides a route to benzo[b]furan-2(3H)-ones. Previously reported results are used in a comparison of seven O-based directed metalation groups in reactions with several electrophiles. The described methodology is useful for the preparation of 1,2,3-substituted aromatic compounds.

Ni(0)-Catalyzed Cross Coupling of Aryl O-Carbamates and Aryl Triflates with Grignard Reagents. Directed Ortho Metalation-Aligned Synthetic Methods for Polysubstituted Aromatics via a 1,2-Dipole Equivalent

The first Ni(0)-catalyzed cross-coupling reactions of aryl O-carbamates and aryl triflates with Grignard reagents (Scheme I) to give diversely polysubstituted aromatics 2d and 2e (Table I) which feature regiospecificity based on directed ortho metalation (carbamate), minimal β-hydride elimination (triflate), and dependence on steric and electronic effects are described.

The Directed Ortho Lithiation of O-Aryl Carbamates. An Anionic Equivalent of the Fries Rearrangement

Ortho-Lithiated O-aryl carbamates 3 constitute new synthetic intermediates which by treatment with a variety of electrophiles lead to ortho-substituted carbamates 4 and by rearrangement provide salicylamides 6.