The employment of α-iminometallocarbenes to construct valuable N-containing compounds has attracted significant research interest.Herein,the nucleophilic addition of nitrosoarenes with the α-imino rhodium carbene sp...The employment of α-iminometallocarbenes to construct valuable N-containing compounds has attracted significant research interest.Herein,the nucleophilic addition of nitrosoarenes with the α-imino rhodium carbene species(I),which is derived from Rh_(2)(ll)-catalyzed denitrogenation of 3-diazoindolin-2-imines,to produce synthetically useful 2-iminoindolin-nitrones is described.Mechanistically,the N-attack of nitrosoarenes with the carbene site of I is proposed.For the analogous Rh_(2)(ll)-catalyzed reaction of nitrosoarenes with N-sulfonyl-1,2,3-triazoles reported by Li and co-workers(Org.Lett.2014,16,6394),however,the O-attack of nitrosoarenes with the carbene site of α-imino rhodium carbene species(II)is more favorable to occur than the N-attack.The subsequent transformation to yield the product of N-acylamidines is rationalized based on computational studies.The mechanistic differ-ences for the reactions of nitrosoarenes with a-imino rhodium carbene species I and II are discussed.展开更多
An uncatalyzed and easily accessible synthetic approach for the preparation of 3-aroylindoles was investigated using nitrosoarenes and aromatic terminal ethynyl ketones. Indole derivatives were produced in good yields...An uncatalyzed and easily accessible synthetic approach for the preparation of 3-aroylindoles was investigated using nitrosoarenes and aromatic terminal ethynyl ketones. Indole derivatives were produced in good yields and excellent regioselectivity. Functionalizations of the indole products were carried out affording highly valuable and versatile compounds. The indolization protocol was studied as a fundamental step for the preparation of pravadoline and 1-butyl-3-(1-naphthoyl)indole (JWH-073), bioactive molecules showing antinociceptic properties.展开更多
Nitroso compounds have emerged as highly valuable reaction partners or reagents in organic synthesis due to their rich reactivity.The versatile profile of these compounds allows them to function as electrophiles,nucle...Nitroso compounds have emerged as highly valuable reaction partners or reagents in organic synthesis due to their rich reactivity.The versatile profile of these compounds allows them to function as electrophiles,nucleophiles,diradicals,and radical acceptors in diverse transformations.In recent years,notable progress has been made in harnessing photochemical reactions with nitroso compounds to prepare N,O-containing structures using mild and eco-friendly conditions.Various nitroso compounds like nitrosoarenes,acyloxy nitroso compounds,N-nitrosoamines and nitrites have received significant attention for their ability to introduce NO moieties into complex molecules that are otherwise difficult to access.In this review,we provide an overview of the recent advancements in the visible light-induced conversion of nitroso compounds,with particular emphasis on their role as bifunctional reagents and acceptors of radicals,carbenes and nitrenes.展开更多
基金the National Natural Science Foundation of China(No.21973068)the Project of Scientific and Technologic Infrastructure of Suzhou(No.SZS201708)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)for financial support.
文摘The employment of α-iminometallocarbenes to construct valuable N-containing compounds has attracted significant research interest.Herein,the nucleophilic addition of nitrosoarenes with the α-imino rhodium carbene species(I),which is derived from Rh_(2)(ll)-catalyzed denitrogenation of 3-diazoindolin-2-imines,to produce synthetically useful 2-iminoindolin-nitrones is described.Mechanistically,the N-attack of nitrosoarenes with the carbene site of I is proposed.For the analogous Rh_(2)(ll)-catalyzed reaction of nitrosoarenes with N-sulfonyl-1,2,3-triazoles reported by Li and co-workers(Org.Lett.2014,16,6394),however,the O-attack of nitrosoarenes with the carbene site of α-imino rhodium carbene species(II)is more favorable to occur than the N-attack.The subsequent transformation to yield the product of N-acylamidines is rationalized based on computational studies.The mechanistic differ-ences for the reactions of nitrosoarenes with a-imino rhodium carbene species I and II are discussed.
文摘An uncatalyzed and easily accessible synthetic approach for the preparation of 3-aroylindoles was investigated using nitrosoarenes and aromatic terminal ethynyl ketones. Indole derivatives were produced in good yields and excellent regioselectivity. Functionalizations of the indole products were carried out affording highly valuable and versatile compounds. The indolization protocol was studied as a fundamental step for the preparation of pravadoline and 1-butyl-3-(1-naphthoyl)indole (JWH-073), bioactive molecules showing antinociceptic properties.
基金supported by the National Natural Science Foundation of China(22301292,21971001)the Distinguished Young Research Project of Anhui Higher Education Institution(2023AH020003)Armido Studer thanks the Deutsche Forschungsgemeinschaft(DFG)for funding(STU 280/92-1)。
文摘Nitroso compounds have emerged as highly valuable reaction partners or reagents in organic synthesis due to their rich reactivity.The versatile profile of these compounds allows them to function as electrophiles,nucleophiles,diradicals,and radical acceptors in diverse transformations.In recent years,notable progress has been made in harnessing photochemical reactions with nitroso compounds to prepare N,O-containing structures using mild and eco-friendly conditions.Various nitroso compounds like nitrosoarenes,acyloxy nitroso compounds,N-nitrosoamines and nitrites have received significant attention for their ability to introduce NO moieties into complex molecules that are otherwise difficult to access.In this review,we provide an overview of the recent advancements in the visible light-induced conversion of nitroso compounds,with particular emphasis on their role as bifunctional reagents and acceptors of radicals,carbenes and nitrenes.
