- A Catalyst-Free Amination of Functional Organolithium Reagents by Flow Chemistry
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Reported is the electrophilic amination of functional organolithium intermediates with well-designed aminating reagents under mild reaction conditions using flow microreactors. The aminating reagents were optimized to achieve efficient C?N bond formation without using any catalyst. The electrophilic amination reactions of functionalized aryllithiums were successfully conducted under mild reaction conditions, within 1 minute, by using flow microreactors. The aminating reagent was also prepared by the flow method. Based on stopped-flow NMR analysis, the reaction time for the preparation of the aminating reagent was quickly optimized without the necessity of work-up. Integrated one-flow synthesis consisting of the generation of an aryllithium, the preparation of an aminating reagent, and their combined reaction was successfully achieved to give the desired amine within 5 minutes of total reaction time.
- Kim, Heejin,Yonekura, Yuya,Yoshida, Jun-Ichi
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supporting information
p. 4063 - 4066
(2018/03/21)
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- Perfluoroalkanosulfonyl fluoride: A useful reagent for dehydration of aldoximes to nitriles
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The reaction of a variety of aldoximes with perfluoroalkanosulfonyl fluoride in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in dichloromethane smoothly generated the corresponding nitriles in 70%-95% yields.
- Yan, Zhao-Hua,Tian, Huan,Zhao, Dong-Dong,Jin, Hong-Ai,Tian, Wei-Sheng
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- Convenient conversion of aldoximes into nitriles with N-chlorosuccinimide and pyridine
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Benzaldehyde oximes substituted with electron-donating groups are dehydrated to the corresponding benzonitriles by N-chlorosuccinimide/pyridine in acetonitrile. Benzaldehyde oxime itself and alkanal oximes afford the corresponding aldehydes. Thieme Stuttgart.
- Gucma, Miroslaw,Golebiewski, W. Marek
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scheme or table
p. 1997 - 1999
(2009/04/03)
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- (t-Bu)2PN=P(i-BuNCH2CH2)3N: New efficient ligand for palladium-catalyzed C-N couplings of aryl and heteroaryl bromides and chlorides and for vinyl bromides at room temperature
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(Chemical Equation Presented) By employing Pd(OAc)2, Cs 2CO3, or NaOH, and the new ligand (t-Bu) 2PN=P(i-BuNCH2CH2)3N (3a), an electronically diverse array of aryl bromides and chlorides possessing base-sensitive substituents (nitro, ester, and keto) provide coupling products with bulky aryl amines in good to excellent yields. Aryl halides possessing other functional groups including cyano, amino, trifluoromethyl, and phenol, coupled with equal ease, producing highly functionalized amines in good to excellent yields. Moreover, an aryl chloro group can be preserved in the presence of a bromo substituent under our reaction conditions. BOC-protected amines also participated efficiently. Heterocyclic bromides and chlorides underwent clean couplings with amines in excellent yields. An important strength of our protocol is the use of lower palladium loadings than those reported earlier, without compromising yields. The air-stable palladium complex (η3-cinnamyl)PdCl·(3a) (5) was also employed successfully in C-N coupling reactions while the crotyl analogue was less efficacious. The 3a/Pd(OAc)2 catalyst system promotes, for the first time, efficient coupling of vinyl bromides with a variety of amines to produce imines and enamines at room temperature.
- Reddy, Ch. Venkat,Kingston, Jesudoss V.,Verkade, John G.
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p. 3047 - 3062
(2008/09/19)
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- P[N(i-Bu)CH2CH2]3N: A versatile ligand for the Pd-catalyzed amination of aryl chlorides
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(Matrix presented) Palladium-catalyzed amination reactions of aryl chlorides with amines proceeded in the presence of the bicyclic triaminophosphine P[N(i-Bu)CH2CH2]3N to afford the corresponding arylamines in good to excellent yields. Electron-poor, electron-neutral, and electron-rich aryl chlorides all participated with equal ease.
- Urgaonkar, Sameer,Nagarajan,Verkade, John G.
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p. 815 - 818
(2007/10/03)
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