Unexpected regioselectivity in the synthesis of pyranonaphthoquinone via the Diels-Alder reaction.
The unusual regioselectivity in the Diels-Alder reactions of pyranoquinone 1 with (4,4-dimethoxybuta-1,3-dien-2-yloxy)trimethylsilane 2 are explored by both computations and experiments. The regioselectivity is controlled by the electrostatic interaction of the lactone ring-oxygen and the vicinal quinone oxygen on the transition structure, which can be tuned by the terminal methyl group of the butadienes.
Cui
Yi
Y
Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education and Beijing National Laboratory for Molecular Science (BNLMS), College of Chemistry, Peking University, Beijing 100871, China.
Jiang
Hao
H
Li
Zhengtao
Z
Wu
Na
N
Yang
Zhen
Z
Quan
Junmin
J
D007783:Lactones / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D009285:Naphthoquinones / Q000138:chemical synthesis* / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D011714:Pyrans / Q000138:chemical synthesis* / Q000737:chemistry*; D055672:Static Electricity; D013237:Stereoisomerism; D013379:Substrate Specificity
D007783:Lactones; D009285:Naphthoquinones; D011714:Pyrans; D010100:Oxygen