79615-68-2

Upstream product

• 623-03-0 4-Cyanochlorobenzene 
• 75-84-3 2,2-dimethyl-propanol-1 
• 623-00-7 4-bromobenzenecarbonitrile 
• 193001-31-9 [1,1'-bis(diphenylphosphino)ferrocene]Pd(p-benzonitrile)[OCH₂C(CH₃)3] 
• 874-90-8 4-methoxybenzonitrile 

Downstream Products

• 210694-04-5 4-(2,2-dimethylpropoxy)benzaldehyde 
• 79615-46-6 4-[4-(2,2-Dimethyl-propoxy)-phenyl]-thiazol-2-ylamine; hydrochloride 
• 79615-90-0 2-Chloro-1-[4-(2,2-dimethyl-propoxy)-phenyl]-ethanone 
• 79615-75-1 1-(4-(neopentyloxy)phenyl)ethan-1-one 

Relevant academic research and scientific papers

Phosphazene Base tBu-P4 Catalyzed Methoxy–Alkoxy Exchange Reaction on (Hetero)Arenes

The organic superbase tBu-P4 catalyzes methoxy-alkoxy exchange reactions on (hetero)arenes with alcohols. The catalytic reaction proceeded efficiently with electron-deficient methoxy(hetero)arenes as well as with a variety of alcohols, including 3-amino-1-propanol, β-citronellol, menthol, and cholesterol. An intramolecular version of this reaction furnished six- and seven-membered ring compounds.

Electronic dependence of C-O reductive elimination from palladium (aryl)neopentoxide complexes

Thermal decomposition of the palladium (aryl)neopentoxide complexes [P-P]Pd(Ar)OCH2CMe3 [P-P =Tol-BINAP or BINAP; Ar p-C6H4CHO (1b), p-C6H4COPh (1c), p-C6H4NO2 (1d), o-C6H4NO2 (1e), o-C6H4CN (1F)] possessing substituents on the palladium-bound aryl group suitable for delocalization of negative charge led to quantitative (≤95%) formation of aryl ether without detectable β-hydride elimination. Thermal decomposition of 1b-f obeyed first-order kinetics, and the rate of reductive elimination decreased in the order o-NO2 > p-NO2 > p-CHO > p-COPh > o-CN. Conversely, thermal decomposition of the related derivatives [P-P]Pd(Ar)OCH2CMe3 [P-P = Tol-BINAP or BINAP; Ar p-C6H4Cl (1g), m-C6H4NO2 (1h), m-C6H4CN (1i)] which did not possess a resonance stabilizing group on the palladium-bound aryl group led to no detectable formation of aryl ether. These and related data point to the buildup of negative charge in the palladium-bound aryl group in the transition state for C-O reductive elimination and are consistent with a mechanism initiated by inner-sphere nucleophilic attack of the alkoxide ligand at the ipso-carbon atom of the palladium-bound aryl group through a zwitterionic Meisenheimer-type intermediate or transition state.