Photomediated ring contraction of saturated heterocycles

doi:10.1126/science.abi7183

GSTDTAP > 气候变化

DOI	10.1126/science.abi7183
	Photomediated ring contraction of saturated heterocycles
	Justin Jurczyk; Michaelyn C. Lux; Donovon Adpressa; Sojung F. Kim; Yu-hong Lam; Charles S. Yeung; Richmond Sarpong
	2021-08-27
发表期刊	Science
出版年	2021
英文摘要	Manipulation of carbon–nitrogen rings is integral to the synthesis of numerous pharmaceutical and agrochemical compounds. Jurczyk et al. report that photoexcitation of carbonyl-substituted cyclic amines can shift the nitrogen from inside to outside the ring framework. The reaction appears to proceed through a 1,5-hydrogen shift to the electronically excited carbonyl, which sets in motion the subsequent carbon–nitrogen and carbon–carbon bonding rearrangements. Several oxygen and sulfur heterocycles were applicable as well. Addition of a chiral phosphoric acid catalyst rendered the reaction asymmetric. Science , abi7183, this issue p. [1004][1] Saturated heterocycles are found in numerous therapeutics and bioactive natural products and are abundant in many medicinal and agrochemical compound libraries. To access new chemical space and function, many methods for functionalization on the periphery of these structures have been developed. Comparatively fewer methods are known for restructuring their core framework. Herein, we describe a visible light–mediated ring contraction of α-acylated saturated heterocycles. This unconventional transformation is orthogonal to traditional ring contractions, challenging the paradigm for diversification of heterocycles including piperidine, morpholine, thiane, tetrahydropyran, and tetrahydroisoquinoline derivatives. The success of this Norrish type II variant rests on reactivity differences between photoreactive ketone groups in specific chemical environments. This strategy was applied to late-stage remodeling of pharmaceutical derivatives, peptides, and sugars. [1]: /lookup/doi/10.1126/science.abi7183
领域	气候变化 ; 资源环境
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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/336662
专题	气候变化资源环境科学
推荐引用方式 GB/T 7714	Justin Jurczyk,Michaelyn C. Lux,Donovon Adpressa,et al. Photomediated ring contraction of saturated heterocycles[J]. Science,2021.
APA	Justin Jurczyk.,Michaelyn C. Lux.,Donovon Adpressa.,Sojung F. Kim.,Yu-hong Lam.,...&Richmond Sarpong.(2021).Photomediated ring contraction of saturated heterocycles.Science.
MLA	Justin Jurczyk,et al."Photomediated ring contraction of saturated heterocycles".Science (2021).