2018-89-5

Upstream product

• 2243-83-6 2-naphthaloyl chloride 
• 13577-85-0 N,N-dimethyl-2-naphthylcarboxamide 
• 35480-23-0 2-(acetoxymethyl)naphthalene 
• 100-46-9 benzylamine 
• 110-91-8 morpholine 

Downstream Products

• 1467-79-4 NCNMe₂ 
• 91-57-6 2-Methylnaphthalene 
• 66-99-9 β-naphthaldehyde 
• 21969-45-9 1,2-bis(2-naphthyl)ethane 
• 581-96-4 2-naphthylacetic acid 
• 158535-61-6 phenyl 2-(naphthalen-2-yl)acetate 
• 53342-32-8 2-naphthylacetic acid benzyl ester 
• 955819-30-4 2-(naphthalen-2-yl)-N-phenylacetamide 
• 1429517-99-6 N,N-dimethyl-1-(3-phenylnaphthalen-2-yl)methanamine 
• 32891-91-1 2-(4-methoxy-benzyl)-naphthalene 

Relevant academic research and scientific papers

Deoxygenative hydroboration of primary, secondary, and tertiary amides: Catalyst-free synthesis of various substituted amines

Transformation of relatively less reactive functional groups under catalyst-free conditions is an interesting aspect and requires a typical protocol. Herein, we report the synthesis of various primary, secondary, and tertiary amines through hydroboration of amides using pinacolborane under catalyst-free and solvent-free conditions. The deoxygenative hydroboration of primary and secondary amides proceeded with excellent conversions. The comparatively less reactive tertiary amides were also converted to the corresponding N,N-diamines in moderate yields under catalyst-free conditions, although alcohols were obtained as a minor product.

Mechanistic Insights on Reduction of Carboxamides by Diisobutylaluminum Hydride and Sodium Hydride?Iodide Composite

The reaction mechanisms on reduction of tertiary carboxamides by diisobutylaluminum hydride (DIBAL) and sodium hydride (NaH)-sodium iodide (NaI) composite were elucidated by the computational and experimental approaches. Reduction of N,N-dimethyl carboxamides with DIBAL provides the corresponding amines, whereas that with the NaH?NaI composite exclusively forms aldehyde even at high reaction temperature. DFT calculations revealed that dimeric structural nature of DIBAL and Lewis acidity on its Al center play crucial role to decompose the tetrahedral anionic carbinol amine intermediate through C?O bond cleavage. On the other hand, in the reduction with the NaH?NaI composite, the resulting tetrahedral anionic carbinol amine intermediate could be kept stable, thus providing aldehydes as a sole product by the aqueous workup.

Controlled Reduction of Carboxamides to Alcohols or Amines by Zinc Hydrides

New protocols for controlled reduction of carboxamides to either alcohols or amines were established using a combination of sodium hydride (NaH) and zinc halides (ZnX2). Use of a different halide on ZnX2 dictates the selectivity, wherein the NaH-ZnI2 system delivers alcohols and NaH-ZnCl2 gives amines. Extensive mechanistic studies by experimental and theoretical approaches imply that polymeric zinc hydride (ZnH2)∞ is responsible for alcohol formation, whereas dimeric zinc chloride hydride (H?Zn?Cl)2 is the key species for the production of amines.

DMF as a dimethylamine equivalent in the palladium-catalyzed nucleophilic substitution of naphthylmethyl and allyl acetates

Naphthylmethyl acetates 1a and 2a were substituted by morpholine in DMPU in the presence of 2 mol% of [Pd(dba)2 + 1.5 dppe] to give products 9-10 in 66-70% isolated yield. In DMF in the presence of benzylamine, N,N-dimethylnaphthylmethylamines 11-12 were produced in 78-85% isolated yield.