Zn-mediated decarboxylative carbagermatranation of aliphatic N-hydroxyphthalimide esters: evidence for an alkylzinc
Wei-Tao Jiang1, Shuo Yang1, Meng-Yu Xu1
1Department of Chemistry , University of Science and Technology of China , Hefei 230026 , China .
Abstract:
Alkyl nucleophiles synthesized by decarboxylation of the corresponding N-hydroxyphthalimide esters (NHP esters) would inherit the complex structure of natural carboxylic acids and result in useful cross-coupling fragments. Herein, we report the synthesis of alkyl carbagermatranes via Zn-mediated decarboxylation of NHP esters without Ni catalysis or photocatalysis. Mechanistic studies indicate that an alkyl zinc intermediate was involved; however, the generation of alkyl zinc will be inhibited in the presence of Ni. Hence, this study provides valuable resolution to the perplexing problem about whether organozinc was involved in recently emerging catalytic systems of NHP ester-Zn. Meanwhile, alkyl zinc reagents from NHP esters are compatible with aryl/alkyl bromides and iodides; therefore the scope of carbagermatranation in this work precedes that of in situ-generated organozinc from alkyl halides.
More Related Videos
Related Concept Videos
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
Alkylation of β-Diester Enolates: Malonic Ester Synthesis
Carboxylic Acids to Methylesters: Alkylation using Diazomethane
Acid Halides to Alcohols: Grignard Reaction
Grignard reagents are a source of carbanions and function as nucleophiles. The mechanism begins with the nucleophilic attack by the carbanion at the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs,...
Nitriles to Ketones: Grignard Reaction
The mechanism begins with a nucleophilic attack by the Grignard...
Aldehydes and Ketones to Alkenes: Wittig Reaction Mechanism
The reaction begins with the nucleophilic addition between a phosphorus ylide and the carbonyl compound. Due to its carbanionic character, phosphorus ylide acts as a strong nucleophile and attacks the electrophilic carbonyl group. This generates a charge-separated dipolar intermediate called betaine. The negatively charged oxygen atom and...


