Photocycloaddition of four-carbon-tethered pyridones. Intramolecular hydrogen bonding and facilitated amide hydrolysis by a proximal secondary alcohol.
Four-carbon-tethered pyridones undergo photocycloaddition to give exclusively trans-[4 + 4] products. The presence of a tether alcohol engenders a solvent-dependent diastereoselectivity for the cycloaddition by intramolecular hydrogen bonding to the adjacent pyridone. Following cycloaddition, the alcohol can deliver a carbonyl group to the proximal, hindered amide nitrogen, leading to a very facile amide hydrolysis.
Zhu
Man
M
Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122, USA.
Qiu
Zhilei
Z
Hiel
Gary P
GP
Sieburth
Scott McN
SM
D000438:Alcohols / Q000737:chemistry*; D000577:Amides / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D006860:Hydrogen Bonding; D006868:Hydrolysis; D007659:Ketones / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D010777:Photochemistry; D011725:Pyridines / Q000737:chemistry / Q000528:radiation effects; D011728:Pyridones / Q000737:chemistry* / Q000528:radiation effects; D012997:Solvents; D013237:Stereoisomerism
D000438:Alcohols; D000577:Amides; D007659:Ketones; D011725:Pyridines; D011728:Pyridones; D012997:Solvents