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Intramolecular [2+2] Photocycloaddition of 3‐ and 4‐(But‐3‐enyl)oxyquinolones: Influence of the Alkene Substitution Pattern, Photophysical Studies, and Enantioselective Catalysis by a Chiral Sensitizer
Author(s) -
Maturi Mark M.,
Wenninger Matthias,
Alonso Rafael,
Bauer Andreas,
Pöthig Alexander,
Riedle Eberhard,
Bach Thorsten
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201300203
Subject(s) - chemistry , diradical , alkene , intramolecular force , enantioselective synthesis , diastereomer , photochemistry , stereochemistry , enantiomer , cyclobutane , cycloaddition , medicinal chemistry , catalysis , organic chemistry , singlet state , ring (chemistry) , physics , nuclear physics , excited state
Abstract The intramolecular [2+2] photocycloaddition of four 4‐(but‐3‐enyl)oxyquinolones (substitution pattern at the terminal alkene carbon atom: CH 2 , Z ‐CHEt, E ‐CHEt, CMe 2 ) and two 3‐(but‐3‐enyl)oxyquinolones (substitution pattern: CH 2 , CMe 2 ) was studied. Upon direct irradiation at λ =300 nm, the respective cyclobutane products were formed in high yields (83–95 %) and for symmetrically substituted substrates with complete diastereoselectivity. Substrates with a Z ‐ or E ‐substituted terminal double bond showed a stereoconvergent reaction course leading to mixtures of regio‐ and diastereomers with almost identical composition. The mechanistic course of the photocycloaddition was elucidated by transient absorption spectroscopy. A triplet intermediate was detected for the title compounds, which–in contrast to simple alkoxyquinolones such as 3‐butyloxyquinolone and 4‐methoxyquinolone–decayed rapidly ( τ ≈1 ns) through cyclization to a triplet 1,4‐diradical. The diradical can evolve through two reaction channels, one leading to the photoproduct and the other leading back to the starting material. When the photocycloaddition was performed in the presence of a chiral sensitizer (10 mol %) upon irradiation at λ =366 nm in trifluorotoluene as the solvent, moderate to high enantioselectivities were achieved. The two 3‐(but‐3‐enyl)oxyquinolones gave enantiomeric excesses ( ee s) of 60 and 64 % at −25 °C, presumably because a significant racemic background reaction occurred. The 4‐substituted quinolones showed higher enantioselectivities (92–96 % ee at −25 °C) and, for the terminally Z ‐ and E ‐substituted substrates, an improved regio‐ and diastereoselectivity.