- Palladium-Catalyzed Carbonylative Coupling Reactions of N,N-Bis(methanesulfonyl)amides through C–N Bond Cleavage
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Palladium-catalyzed carbonylative coupling reactions of various N,N-bis(methanesulfonyl)amides with arylboronic acids through C–N bond cleavage were carried out. The reactions proceeded under mild conditions in a short period of time without any additives to afford a wide range of unsymmetrical aryl ketones in excellent yields. This is the first example of a carbonylative coupling reaction using N,N-bis(methanesulfonyl)amide as a coupling substrate.
- Lim, Minkyung,Kim, Hyeji,Ban, Jaeyoung,Son, Junghan,Lee, Jae Kyun,Min, Sun-Joon,Lee, Sang Uck,Rhee, Hakjune
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- Polysulfonylamines, XXXVI, Trimethylsilyl Dimesylamine: Preparation, NMR-Spectroscopic Characterization, and Reactivity as a Silylating Agent
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(CH3)3SiN(SO2CH3)2 (1), m.p. 69-70 deg C, is obtained by metathesis of AgN(SO2CH3)2 with (CH3)3SiCl (improvement of a known procedure) or, more conveniently, by silylation of HN(SO2CH3)2 with 2NH.The (1)H, (13)C and (29)Si NMR solution spectra and the (29)Si NMR solid-state spectrum suggest the constitution of 1 in solution (CDCl3, CD2Cl2, CDCl2-CDCl2) to be an equilibrium mixture of the N-silylated form (CH3)3Si-N(SO2CH3)2 (I) and the O-silylated form (CH3)3Si-O-S(O)(CH3) = NSO2CH3 (II) in a molar ratio of 2:1 at room temperature, whereas in the known crystal structure of 1 only form I is present.The solid-state NMR experiment acted as a bridge between X-ray crystallography and solution-state NMR, enabling assignments of the resonances to be made with confidence to the tautomers.At room temperature, form II undergoes a rapid intramolecular 1.5-migration of silicon between oxygen centers of the two sulfonyl groups.As shown by kinetic measurements using (1)H NMR spectroscopy, 1 is a highly reactive agent for silylating ketones in the presence of triethylamine.Hydroxy and thiol functions, even when sterically hindered, are silylated by 1 in uncatalyzed reactions.It is further shown that HN(SO2CH3)2 is an efficient catalyst for silylations with 2NH. Key words: Polysulfonylamines, Trimethylsilyl Dimesylamine, N,O- and O,O-Silyl Migration, Silylation of Hydroxy and Thiol Functions, Solid State (29)Si NMR
- Blaschette, Armand,Wieland, Elke,Hamann, Thomas,Harris, Robin K.
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p. 1693 - 1700
(2007/10/02)
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- Polysulfonylamines, XII. N-Acyl Dimesylamines (Carboxylic Acid N,N-Dimesylamides)
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N-Acyl dimesylamines RC(O)N(SO2CH3)2 (3) have been prepared by reacting solid KN(SO2CH3)2 with neat liquid RC(O)Cl at 70-90 deg C or solutions of AgN(SO2CH3)2 in methyl cyanide with RC(O)Cl at room temperature .Addition of chlorine or bromine to 3 (R = CH2=CH) affords the corresponding compounds 3 with R = CH2Cl-CHCl and CH2Br-CHBr, respectively.By hydrolysis of 3 (R = CCl3), CCl3C(O)NHSO2CH3 (5) is obtained.The new compounds 3 and 5 are characterized by spectroscopic (NMR, MS) and analytical methods. - Keywords: N-Acyl Dimesylamines, Potassium and Silver Dimesylaminides, Acyl Chlorides
- Blaschette, Armand,Safari, Firouz,Linoh, Karin,Koch, Dietrich
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p. 1495 - 1500
(2007/10/02)
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