85370-88-3

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 1696-17-9 N,N-diethylbenzamide 
• 62924-92-9 N,N-diethyl-2-(trimethylsilyl)benzamide 

Downstream Products

• 97567-48-1 C₁₁H₁₃⁽²⁾H₂NO 
• 85370-72-5 2,6-dibromo-N,N-diethylbenzamide 

Relevant academic research and scientific papers

One-Pot Twofold Unsymmetrical C-Si Bond 2,6-Bifunctionalization of Arenes via Sequential [1,4]-Csp2 to O-Silyl Migration

Twofold unsymmetrical C-Si bond bifunctionalization of 2,6-di(trimethylsilyl) benzyl alcohols has been achieved in one pot via sequential [1,4]-Csp2 to O-silyl migration. The hydroxyl group functions as an "on-off-on" switch to control two successive silyl migrations, and 4,7-dimethyl-o-phenanthroline ligand favors cleavage of the endocyclic C-Si bond. Diverse Csp3/Csp3 or Csp2/Csp3 electrophiles can be installed at the 2- and 6-positions. This approach was used to chemoselectively functionalize the three C-Si bonds of 2,4,6-tri(trimethylsilyl) benzyl alcohol, transforming it into isochroman derivatives. The approach even works as a five-component reaction to construct complex symmetric structures.

Chemoselective Reduction of Sterically Demanding N,N-Diisopropylamides to Aldehydes

A sequential one-pot process for chemoselectively reducing sterically demanding N,N-diisopropylamides to aldehydes has been developed. In this reaction, amides are activated with EtOTf to form imidates, which are reduced with LiAlH(OR)3 [R = t-Bu, Et] to give aldehydes by hydrolysis of the resulting hemiaminals. The non-nucleophilic base 2,6-DTBMP remarkably improves reaction efficiency. The combination of EtOTf/2,6-DTBMP and LiAlH(O-t-Bu)3 was found to be optimal for reducing alkyl, alkenyl, alkynyl, and 2-monosubstituted aryl N,N-diisopropylamides. In contrast, EtOTf and LiAlH(OEt)3 in the absence of base were found to be optimal for reducing extremely sterically demanding 2,6-disubstituted N,N-diisopropylbenzamides. The reaction tolerates various reducible functional groups, including aldehyde and ketone. 1H NMR studies confirmed the formation of imidates stable in water. The synthetic usefulness of this methodology was demonstrated with N,N-diisopropylamide-directed ortho-metalation and C-H bond activation.

DILITHIATED SYNTHONS OF TERTIARY BENZAMIDES, PHTHALAMIDES, AND O,O'-ARYL DICARBAMATES

Dilithiated species 1, 2, and 3, generated by metal-halogen exchange and directed ortho metalation, undergo reaction with electrophiles to afford, in high yield, polysubstituted aromatics 6, 7, and 8 respectively; 9 is formed via a bis anionic Fries rearr

Directed Metalation of Tertiary Benzamides. Silicon Protection of Ortho Sites and Ortho Methyl Groups

Metalation of 2-trimethylsilyl or 2-bis(trimethylsilyl)methyl benzamides occurs selectively at the 6-position, providing regiospecific routes to various trisubstituted benzenes.