Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 57, Issue 8, Pages 2134-2138Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201711873
Keywords
cycloaddition; dearomatization; indoles; palladium; stereodivergent reactions
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Funding
- National Key R&D Program of China [2016YFA0202900]
- National Basic Research Program of China [2015CB856600]
- NSFC [21332009, 21572252]
- Program of Shanghai Subject Chief Scientist [16XD1404300]
- Strategic Priority Research Program [XDB20000000]
- Key Research Program of Frontier Sciences of CAS [QYZDY-SSW-SLH012]
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A stereodivergent synthesis of tetrahydrofuroindoles through palladium-catalyzed asymmetric dearomative formal [3+2] cycloaddition of nitroindoles with epoxybutenes was developed. The polarity of the solvent was found to play a key role in the diastereoselectivity. In toluene, good to excellent yields (70-99%), diastereoselectivity (87/13- > 95/5 d.r.), and enantioselectivity (85/15-94/6 e.r.) were obtained, regardless of the properties of the substituents on nitroindoles. In acetonitrile, tetrahydrofuroindoles of a different diastereoisomer were produced with good to excellent yields (75-98%) and stereoselectivity (78/22-93/7 d.r., 93/7-99/1 e.r.). Mechanistic studies were conducted to illustrate the origin of the diastereodivergency. The kinetic experiments indicate that the rate-determining step of this reaction is different in different solvents. ESI-MS experiments also support the existence of key palladium complex intermediates and the catalytic cycle of the reaction.
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