Regioselective Diels-Alder cycloadditions and other reactions of 4,5-, 5,6-, and 6,7-indole arynes

被引:40
作者
Brown, Neil [1 ,2 ]
Luo, Diheng [1 ]
Velde, David Vander [2 ]
Yang, Shaorong [1 ]
Brassfield, Allen [1 ]
Buszek, Keith R. [1 ,2 ]
机构
[1] Univ Missouri, Dept Chem, Spencer Chem Labs 205, Kansas City, MO 64110 USA
[2] Univ Kansas, Ctr Excellence Chem Methodol & Lib Dev, Lawrence, KS 66045 USA
基金
美国国家卫生研究院;
关键词
2-SUBSTITUTED FURANS; TELEOCIDIN; (+/-)-CIS-TRIKENTRIN-B; DERIVATIVES; TRIFLATE; PHENOLS; BENZYNE;
D O I
10.1016/j.tetlet.2008.10.086
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The regioselectivity of Diels-Alder cycloadditions of indole arynes (indolynes) at all three benzenoid positions was examined. Cycloadditions with the 45-and 5,6-indolynes, derived via metal-halogen exchange from the corresponding o-dibromo indoles, showed essentially no selectivity with 2-t-butylfuran. in contrast, the 6,7-indolyne displayed virtually complete preference for the more sterically congested cycloadduct. This same cycloadduct undergoes a facile acid-catalyzed rearrangement to afford the annulated enone, or alternatively, undergoes hydrolysis and oxidation in the presence of air to give the indolobenzoquinone. The 5,6-difluoroindoles show anomalous behavior and give either 5-fluoro-6,7-indolynes with n-BULi in ether, or 5,6-indolynes with n-BuLi in toluene. We have also demonstrated that benzenoid indolynes can be easily and conveniently generated by the fluoride-induced decomposition of o-trimethylsilyl triflates. (C) 2008 Elsevier Ltd. All rights reserved.
引用
收藏
页码:63 / 65
页数:3
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