Directed ortho-Metalation and Anionic ortho-Fries Rearrangement of Polycyclic Aromatic O-Carbamates: Regioselective Synthesis of Substituted Chrysenes,The Journal of Organic Chemistry

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Directed ortho-Metalation and Anionic ortho-Fries Rearrangement of Polycyclic Aromatic O-Carbamates: Regioselective Synthesis of Substituted Chrysenes
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2018-03-15 00:00:00 , DOI: 10.1021/acs.joc.7b03210
Sindhu Kancherla ₁ , Marianne Lorentzen ₁ , Victor Snieckus ₂ , Kåre B. Jørgensen ₁

Affiliation

A general method for the regioselective synthesis of a series of ortho-substituted chrysenyl N,N-diethyl-O-carbamates by the directed ortho-metalation (DoM) strategy is reported. The starting O-carbamates were prepared from the corresponding chrysenols, available by oxidative photochemical cyclization or directed remote metalation tactics. Chrysen-1-yl and chrysene-3-yl ring site selectivity of directed ortho-metalation (DoM) and anionic ortho-Fries rearrangement (AoF) protocols, with s-BuLi/TMEDA, followed by electrophilic quench using a selection of electrophiles, were observed, leading to new chrysenyl derivatives. 5-Chrysenyl N,N-diethyl-O-carbamate underwent instant AoF rearrangement even at −100 °C to furnish chrysenyl o-hydroxycarboxamide. Iterative DoM reactions were carried out to gain insight into the regioselectivity factors.

中文翻译：

定向邻-Metalation和阴离子邻多环芳烃-Fries重排Ø -Carbamates：替补Chrysenes的区域选择性合成

报道了通过定向邻位金属化（D o M）策略区域选择性合成一系列邻位取代的N，N-二乙基-O-氨基甲酸酯的一般方法。起始的O-氨基甲酸酯是由相应的酚类化合物制备的，可以通过氧化光化学环化或直接的远程金属化策略获得。屈（chrysene）哌啶-1-基和苯并菲-3-基环部位选择性定向邻-metalation（d Ò M）和阴离子邻-Fries重排（A ö F）协议，与小号观察到-BuLi / TMEDA，随后使用选择的亲电试剂进行亲电淬灭，产生了新的Chrysenyl衍生物。5屈基N，N-二乙基ø -氨基甲酸酯后行瞬间甲ö ˚F即使在-100℃至配料屈重排Ò羟基甲酰胺。进行了反复的D o M反应，以了解区域选择性因素。

更新日期：2018-03-15

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