328534-03-8Relevant academic research and scientific papers
The α-Effect in the Stereochemistry of Kinetic Ketonization of Enols
Zimmerman, Howard E.,Wang, Pengfei
, p. 9226 - 9232 (2007/10/03)
Kinetic control of the stereoselectivity of protonation of enolates and other strongly delocalized anionic species is involved in a large number of organic reactions. Protonation occurring from the less hindered side of the, e.g., enolic system affords the less stable of two diastereomers. However, one apparent discrepancy has been in the synthesis of prostaglandins. The present research deals with the source of this behavior. A curious effect of the substituent at the enolic α carbon was uncovered. In certain instances an α substituent is forced to twist into a conformation blocking the proton donor from its side, thus reversing the stereochemistry of protonation. In the course of this research, a number of five-ring enols of varying structure were investigated. Finally, the ketonization reaction course has been studied theoretically.
Intramolecular reactions of benzylic azides with ketones: Competition between Schmidt and Mannich pathways
Wrobleski,Aube
, p. 886 - 889 (2007/10/03)
The Lewis acid-promoted reactions of benzylic azides with ketones can proceed by two major pathways. The azido-Schmidt reaction involves simple addition of azide to the ketone followed by rearrangement and ring expansion. In addition, benzylic azides can undergo prior rearrangement to afford iminium ions that can subsequently participate in a Mannich reaction. A series of ketones containing an α CH2(CH2)nCH(N3)Ph substituent (n = 1-3) was prepared to investigate the dependence of products on ketone ring size and tether length. For all ketones examined, good yields of bicyclic lactams arising from intramolecular Schmidt reaction were obtained when a four-carbon linker was used (n = 1 in the above formulation), but Mannich products predominated for the longer tethers examined (n = 2, 3).
