Masked o-Benzoquinones in Organic Synthesis

• Published in: Accounts of chemical research Vol. 35; no. 10; pp. 856 - 866
• Main Authors: Liao, Chun-Chen, Peddinti, Rama Krishna
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 01.10.2002
• ISSN: 0001-4842; 1520-4898
• DOI: 10.1021/ar000194n

An account of the synthetic utility of masked o-benzoquinones is provided. The inter- and intramolecular Diels−Alder reactions of in situ generated masked o-benzoquinones produced cycloadducts in excellent selectivities. New synthetic methodologies have been developed for the synthesis of highly substituted ring systems including bicyclo[2.2.2]octenones, oxatricycles, triquinanes, polysubstituted cyclohexanes, and bicyclo[4.2.2]decenones with complete stereocontrol from easily accessible 2-methoxyphenols via the Diels−Alder reaction of masked o-benzoquinones. Other reactions of adducts derived from masked o-benzoquinones are also described. The efficacy of our methodology is demonstrated by several examples of the total synthesis of natural products.