Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 66, Issue 9, Pages 3119-3128Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jo010020z
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- NIGMS NIH HHS [GM59384-21] Funding Source: Medline
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A convenient. synthesis of various substituted hexahydroindolinones has been achieved by an intramolecular Diels-Alder cycloaddition reaction (IMDAF) of furanyl carbamates bearing tethered alkenyl,groups. The initially formed [4 + 2]-cycloadduct undergoes nitrogen-assisted ring opening followed by deprotonation of the resulting zwitterion to give the rearranged ketone. The stereochemical outcome of the IMDAF cycloaddition has the sidearm of the tethered alkenyl group oriented syn with respect to the oxygen bridge. A synthetic route to (+/-)-mesembrane and (+/-)-crinane was accomplished using this methodology. It was possible to carry out a stereoselective reduction of the initially formed hexahydroindolinone ring to produce the cis-3a-aryl-hydroindole skeleton. A related [4 + 2] -cycloaddition/rearrangement sequence was also used for a formal synthesis of the Chinese ornamental orchid (+/-)-dendrobine. The tricylic alkaloid core was formed stereoselectivity fr om the thermolysis of N-[(2-methyl-2-cyclopentenyl)methyl]-N-(4-isopropyl-furan-2-yl)carbamic acid tert-butyl ester. Kende's advanced intermediate 33 was prepared in seven additional steps by standard transformations, thereby completing a formal synthesis of (+/-)-dendrobine.
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