Hanessian Stephen, Tremblay Martin
Department of Chemistry, Université de Montréal, C.P. 6128, Station Centre-ville, Montréal, PQ, H3C 3J7 Canada.
Org Lett. 2004 Dec 9;6(25):4683-6. doi: 10.1021/ol040053b.
[reaction: see text] Five-membered N-Boc acyliminium ions derived from L-pyroglutamic acid harboring 4-butenyl and 4-butynyl tethers undergo Lewis acid-mediated halo and tandem Friedel-Crafts carbocyclization within minutes at -78 degrees C to give stereodefined 6-substituted octahydroindole and hexahydroindole 2-carboxylic acid methyl esters, respectively. The cyclic vinyl bromides are excellent substrates for Pd-catalyzed Suzuki-Miyaura, Heck, and Stille couplings. The method also provides access to enantiopure sp2- and sp3-arylated azabicyclics that are novel and versatile scaffolds for chemical diversification.
[反应：见正文] 源自L-焦谷氨酸的带有4-丁烯基和4-丁炔基连接基的五元N-叔丁氧羰基酰亚胺离子在-78℃下几分钟内经历路易斯酸介导的卤化和串联傅克碳环化反应，分别得到立体专一的6-取代八氢吲哚和六氢吲哚-2-羧酸甲酯。环状乙烯基溴是钯催化的铃木-宫浦、赫克和施蒂勒偶联反应的优良底物。该方法还提供了获得对映体纯的sp2和sp3芳基化氮杂双环化合物的途径，这些化合物是用于化学多样化的新型通用支架。
