Photochemical intermolecular dearomative cycloaddition of bicyclic azaarenes with alkenes

doi:10.1126/science.abg0720

GSTDTAP > 气候变化

DOI	10.1126/science.abg0720
	Photochemical intermolecular dearomative cycloaddition of bicyclic azaarenes with alkenes
	Jiajia Ma; Shuming Chen; Peter Bellotti; Renyu Guo; Felix Schäfer; Arne Heusler; Xiaolong Zhang; Constantin Daniliuc; M. Kevin Brown; Kendall N. Houk; Frank Glorius
	2021-03-26
发表期刊	Science
出版年	2021
英文摘要	The Diels-Alder reaction is widely used to produce six-membered carbon rings from alkenes and dienes. Heteroaromatics such as quinolines resemble dienes in principle, but in practice their pairs of double bonds are inert toward cycloadditions because of aromatic stabilization. Ma et al. report that by using an iridium photosensitizer, they could excite quinolines and related azaarenes to triplet states, thereby disrupting the aromaticity and enabling intermolecular, Diels-Alder–like reactivity toward alkenes (see the Perspective by Schmidt). The reactions proceeded exclusively at the flanking carbons outside the nitrogen-containing ring. Science , this issue p. [1338][1]; see also p. [1313][2] Dearomative cycloaddition reactions represent an ideal means of converting flat arenes into three-dimensional architectures of increasing interest in medicinal chemistry. Quinolines, isoquinolines, and quinazolines, despite containing latent diene and alkene subunits, are scarcely applied in cycloaddition reactions because of the inherent low reactivity of aromatic systems and selectivity challenges. Here, we disclose an energy transfer–mediated, highly regio- and diastereoselective intermolecular [4 + 2] dearomative cycloaddition reaction of these bicyclic azaarenes with a plethora of electronically diverse alkenes. This approach bypasses the general reactivity and selectivity issues, thereby providing various bridged polycycles that previously have been inaccessible or required elaborate synthetic efforts. Computational studies with density functional theory elucidate the mechanism and origins of the observed regio- and diastereoselectivities. [1]: /lookup/doi/10.1126/science.abg0720 [2]: /lookup/doi/10.1126/science.abg7834
领域	气候变化 ; 资源环境
URL	查看原文
引用统计
文献类型	期刊论文
条目标识符	http://119.78.100.173/C666/handle/2XK7JSWQ/321094
专题	气候变化资源环境科学
推荐引用方式 GB/T 7714	Jiajia Ma,Shuming Chen,Peter Bellotti,et al. Photochemical intermolecular dearomative cycloaddition of bicyclic azaarenes with alkenes[J]. Science,2021.
APA	Jiajia Ma.,Shuming Chen.,Peter Bellotti.,Renyu Guo.,Felix Schäfer.,...&Frank Glorius.(2021).Photochemical intermolecular dearomative cycloaddition of bicyclic azaarenes with alkenes.Science.
MLA	Jiajia Ma,et al."Photochemical intermolecular dearomative cycloaddition of bicyclic azaarenes with alkenes".Science (2021).