Organic Chemistry

Base-Mediated Generation of Ketenimines from Ynamides: [3+2] Annulation with Azaallyl Anions.

Authors

Abstract

Under basic conditions and heat, ynamides can serve as precursor to ketenimines, whose synthetic potential is often hampered by their difficulty of acces. Herein, we report that they can undergo a [3+2] cycloaddition with 2-azaallyl anions, obtained from benzylimines under the same reaction conditions. This reaction between two highly reactive intermediates, both generated in situ from bench stable starting materials, gives access to various nitrogen-rich heterocycles. The reaction usually proceeds with excellent diastereoselectivity, in favor of the cis adduct. Deuteration experiments and DFT calculation helped rationalize the regio and stereo-selectivity of the process as well as the formation of side-products.

Content

Thumbnail image of Manuscript3+2.pdf

Supplementary material

Thumbnail image of SupportingInfo3+2.pdf
SupportingInfo3+2
Thumbnail image of Gaussian_output3+2.txt
Gaussian output3+2
Thumbnail image of cmpd_7ac_todeposit.txt
cmpd 7ac todeposit
Thumbnail image of cmpd_6ag_deposit.txt
cmpd 6ag deposit
Thumbnail image of Spectres3+2.pdf
Spectres3+2