Aza-[2,3]-Wittig Sigmatropic Rearrangement of Allylic Tertiary Amines: A Successful Example with High Chirality...

Area of Science:

• Organic Chemistry
• Stereoselective Synthesis

Background:

• Allylic tertiary amines are versatile synthetic intermediates.
• The aza-[2,3]-Wittig rearrangement is a powerful carbon-carbon bond-forming reaction.

Purpose of the Study:

• To report a novel aza-[2,3]-Wittig rearrangement in allylic tertiary N,N-dibenzyl amines.
• To investigate the stereochemical outcome of this transformation.

Main Methods:

• Synthesis of allylic tertiary N,N-dibenzyl amines from (S)-alaninol or (S)-isoleucinol.
• Metalation at the benzylic position using a butyllium/diisopropylamine/potassium t-butoxide mixture.
• Analysis of the reaction products for chirality transfer.

Main Results:

• Successful execution of the aza-[2,3]-Wittig rearrangement.
• High 1,3 transfer of chirality observed.
• Demonstration of the reaction's utility with chiral starting materials.

Conclusions:

• The aza-[2,3]-Wittig rearrangement is a viable method for synthesizing chiral compounds.
• This reaction provides a new pathway for stereoselective synthesis.