An Experimental and Computational Approach to Understanding the Reactions of Acyl Nitroso Compounds in [4 + 2] Cycloadditions

The Journal of Organic Chemistry
Duangduan ChaiyaveijAndrew Whiting

Abstract

Catalytic aerobic oxidation of phenyl hydroxycarbamate 1 and 1-hydroxy-3-phenylurea 2 using CuCl2 and 2-ethyl-2-oxazoline in methanol gave acyl nitroso species in situ, which were trapped in nitroso-Diels-Alder (NDA) reactions with various dienes to afford the corresponding cycloadducts in high yields (90-98%). Competing ene products were also present for dienes containing both alkene π-bonds and allylic σ-bonds, and the ene yields are higher with 1 than with 2. The use of the chiral hydroxamic acid, (R)-1-hydroxy-3-(1-phenylethylurea) 3 (same conditions) gave NDA cycloadducts in high yields (97-99%) with no ene product from 2,3-dimethyl-1,3-butadiene. NDA cycloadducts were not obtained from other hydroxamic acid analogues [RCONHOH (R = PhCH2 4; Ph(CH2)2 5; Ph(CH2)3 6; Ph(CH2)4 7; Ph 8; 2-pyridyl 9; 3-pyridyl 10] with various dienes using copper-oxidation but rather were obtained using sodium periodate, resulting in variable NDA yields (13-51%) from hydroxamic acids 1-10 with cyclohexa-1,3-diene and 2,3-dimethyl-1,3-butadiene (several cycloadducts characterized by X-ray crystallography). The NDA and nitroso-ene reaction pathways of nitroso intermediates with dienes were mapped by DFT computations (B3LYP/6-31G*), which showed th...Continue Reading

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Citations

Jan 21, 2017·Chemical Reviews·Misal Giuseppe Memeo, Paolo Quadrelli
May 23, 2017·Acta Crystallographica. Section E, Crystallographic Communications·Inna S SafyanovaSvitlana V Shyshkina
Jan 14, 2017·Acta Crystallographica. Section E, Crystallographic Communications·Inna S SafyanovaIrina V Omelchenko
Nov 11, 2016·Beilstein Journal of Organic Chemistry·Lucie BrulíkováJan Hlaváč
Jul 31, 2021·Bioorganic Chemistry·Shaun W P ReesLisa I Pilkington

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