15854-87-2Relevant articles and documents
Microwave-assisted trans-halogenation reactions of various chloro-, bromo-, trifluoromethanesulfonyloxy- and nonafluorobutanesulfonyloxy-substituted quinolines, isoquinolines, and pyridines leading to the corresponding iodinated heterocycles
Bissember, Alex C.,Banwell, Martin G.
, p. 4893 - 4895 (2009)
(Chemical Equation Presented) Microwave irradiation of certain chloro-, bromo-, trifluoromethanesulfonyloxy- and nonafluorobutanesulfonyloxy-substituted quinolines in the presence of acetic anhydride and sodium iodide leads, via a trans-halogenation process, to the corresponding iodides in high yield. Related conversions involving pyridines and isoquinolines can also be achieved under similar conditions.
Efficient syntheses of 4-iodopyridine and of 4-pyridylboronic acid pinacol ester
Coudret, Christophe
, p. 3543 - 3547 (1996)
4-Iodopyridine can be prepared in good yield by low temperature diazotation-Sandmeyer reaction of the corresponding amine, then efficiently converted to the air-stable pinacol ester of 4-pyridylboronic acid.
A regioselectively 1,1′,3,3′-tetrazincated ferrocene complex displaying core and peripheral reactivity
Armstrong, David R.,Clegg, William,Hevia, Eva,Honeyman, Gordon W.,Kennedy, Alan R.,McLellan, Ross,Mulvey, Robert E.,Orr, Samantha A.,Parkinson, John A.,Ramsay, Donna L.,Robertson, Stuart D.,Towie, Stephen
, p. 6510 - 6520 (2020/07/15)
Regioselective 1,1′,3,3′-tetrazincation [C-H to C-Zn(tBu)] of ferrocene has been achieved by reaction of a fourfold excess of di-t-butylzinc (tBu2Zn) with sodium 2,2,6,6-tetramethylpiperidide (NaTMP) in hexane solution manifested in the trimetallic iron-sodium-zinc complex [Na4(TMP)4Zn4(tBu)4{(C5H3)2Fe}], 1. X-ray crystallographic studies supported by DFT modelling reveal the structure to be an open inverse crown in which two [Na(TMP)Zn(tBu)Na(TMP)Zn(tBu)]2+ cationic units surround a {(C5H3)2Fe}4- tetraanion. Detailed C6D6 NMR studies have assigned the plethora of 1H and 13C chemical shifts of this complex. It exists in a major form in which capping and bridging TMP groups interchange, as well as a minor form that appears to be an intermediate in this complicated exchange phenomenon. Investigation of 1 has uncovered two distinct reactivities. Two of its peripheral t-butyl carbanions formally deprotonate toluene at the lateral methyl group to generate benzyl ligands that replace these carbanions in [Na4(TMP)4Zn4(tBu)2(CH2Ph)2{(C5H3)2Fe}], 2, which retains its tetrazincated ferrocenyl core. Benzyl-Na π-arene interactions are a notable feature of 2. In contrast, reaction with pyridine affords the crystalline product {[Na·4py][Zn(py?)2(tBu)·py]}∞, 3, where py is neutral pyridine (C5H5N) and py? is the anion (4-C5H4N), a rare example of pyridine deprotonated/metallated at the 4-position. This ferrocene-free complex appears to be a product of core reactivity in that the core-positioned ferrocenyl anions of 1, in company with TMP anions, have formally deprotonated the heterocycle.
Direct Transformation of Arylamines to Aryl Halides via Sodium Nitrite and N-Halosuccinimide
Mukhopadhyay, Sushobhan,Batra, Sanjay
supporting information, p. 14622 - 14626 (2018/09/21)
A one-pot universal approach for transforming arylamines to aryl halides via reaction with sodium nitrite (NaNO2) and N-halosuccinimide (NXS) in DMF at room temperature under metal- and acid-free condition is described. This new protocol that is complementary to the Sandmeyer reaction, is suggested to involve the in situ generation of nitryl halide induce nitrosylation of aryl amine to form the diazo intermediate which is halogenated to furnish the aryl halide.
Alkali-metal mediated zincation of N-heterocyclic substrates using the lithium zincate complex, (THF)Li(TMP)Zn(tBu)2 and applications in in situ cross coupling reactions
Blair, Victoria L.,Blakemore, David C.,Hay, Duncan,Hevia, Eva,Pryde, David C.
supporting information; experimental part, p. 4590 - 4594 (2011/09/30)
This study investigates the ability of the mixed-metal reagent [Li(TMP)Zn(tBu)2] 1 to promote direct Zn-H exchange reactions (zincations) of a wide range of N-heterocyclic molecules. The generated metallated intermediates from these reactions are intercepted with I2 and some of them are also employed as precursors in Pd-catalysed Negishi cross-coupling applications. A comparison with recent precedents in metallation chemistry reveals that for some of these heterocycles, 1 allows improved conversions, under milder conditions and in certain cases, even gives unique regioselectivities.
