96927-48-9

Upstream product

• 108-86-1 bromobenzene 
• 38227-87-1 2,2,6,6-tetramethylpiperidinyl-lithium 
• 591-50-4 iodobenzene 
• 2557-81-5 pentafluorosulfanylbenzene 
• 768-66-1 2,2,6,6-tetramethyl-piperidine 
• 17763-67-6 Phenyl triflate 
• 100-61-8 N-methylaniline 
• 2564-83-2 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical 
• 140-29-4 phenylacetonitrile 

Relevant academic research and scientific papers

In situ ortho -lithiation/functionalization of pentafluorosulfanyl arenes

A general method for ortho-functionalization of pentafluorosulfanyl arenes has been developed. ortho-Lithiation with lithium tetramethylpiperidide at -60 °C in the presence of silicon, germanium, and tin electrophiles affords trapped products in moderate

1,2-Difunctionalization of Aryl Triflates: A Direct and Modular Access to Diversely Functionalized Anilines

ortho-Amino difunctionalization of aryl triflates has been achieved via a three-component reaction. The cascade reaction proceeds through a zincate base-mediated deprotonative formation of a reactive aryne intermediate, in situ nucleophilic addition, and coupling with electrophilic partners. This strategy leverages the advantageous reactivity of organozincate intermediates, enabling the installation of various functionalities such as amine, azide, oxygen, sulfur, halide, alkynyl, aryl, vinyl, and alkyl groups in a modular manner for the synthesis of diverse aniline skeletons.

Practical and Scalable Synthesis of Borylated Heterocycles Using Bench-Stable Precursors of Metal-Free Lewis Pair Catalysts

A practical and scalable metal-free catalytic method for the borylation and borylative dearomatization of heteroarenes has been developed. This synthetic method uses inexpensive and conveniently synthesizable bench-stable precatalysts of the form 1-NHR2-2-BF3-C6H4, commercially and synthetically accessible heteroarenes as substrates, and pinacolborane as the borylation reagent. The preparation of several borylated heterocycles on 2 and 50 g scales was achieved under solvent-free conditions without the use of Schlenk techniques or a glovebox. A kilogram-scale borylation of one of the heteroarene substrates was also achieved using this cost-effective green methodology to exemplify the fact that our methodology can be conveniently implemented in fine chemical industries.

Replacing C6F5 groups with Cl and H atoms in frustrated Lewis pairs: H2 additions and catalytic hydrogenations

2-(Dialkylamino)phenylboranes containing the BXZ group, where X, Z = C6F5, Cl, and H, were prepared in a few synthetic steps and demonstrated the cleavage of H2 under mild conditions. Depending on the nature of the dialkylamino group, X, and Z, the stability of the produced zwitterionic H2 adducts varies from isolated solids indefinitely stable in an inert atmosphere to those quickly equilibrating with the initial aminoborane and H2. Using a combined experimental/computational approach on a series of isostructural aminoboranes (dialkylamino = 2,2,6,6-tetramethylpiperid-1-yl), it was demonstrated that the electronegativity and the steric effect of the substituents generally follow the trend C6F5 ～ Cl ? H. This observation is useful for designing new FLPs for practical applications. As an example, we demonstrated the hydrogenation of alkynes to cis-alkenes under mild conditions that was catalyzed by a chloro-analogue of the C6F5-substituted aminoborane developed previously. The presence of a BHCl group in the aminochloroboranes or in their H2 adducts features facile redistribution of the H and Cl atoms and the formation of polychloro and polyhydrido species.

Copper(II)-catalyzed reactions of dimethylformamide with phenylacetonitrile and sulfur to form N,N-dimethylthioamides

Novel copper-catalyzed three-component reactions of phenylacetonitrile, sulfur and DMF (dimethyformamide) for the selective preparation of N,N-dimethylthiobenzamide and N,N-dimethyl-2-phenylethanethioamides in yields of up to 96% are described. Copyright

Dimetalation: The acidity of monometalated arenes towards superbasic reagents

Twofold hydrogen/metal interconversions ("dimetalations") can be accomplished with "spiny" arenes (tert-butylbenzene, 1,4-di-tert-butylbenzene, 1,1,3,3-tetramethylindane and congeners) and N,N-crowded anilines (2,2,6,6-tetramethyl-1-phenylpiperidine and N

Formation of 2-substituted Iodobenzenes from Iodobenzene via Benzyne and Ate Complex Intermediates

(Matrix Presented) The generation of benzyne from iodobenzene with lithium tetramethylpiperidide in THF at -40 °C in the presence of lithium amides and ester enolates leads to mixtures in which 2-substituted iodobenzenes are often the major products. These products are obtained by iodine transfer from iodobenzene to the intermediate 2-lithioaromatics. The transfer of iodine occurs via a hypervalent iodine (ate) complex.

Chemistry and Structure of Phenylcubanes

Phenylcubanes show unusual reactivity toward metalation and oxidation.Metalation of 1,4-bis((diisopropylamino)carbonyl)-2,7-diphenylcubane, 1, occurs at the cubane skeleton while oxidation of 1,4-bis((diisopropylamino)methyl)-2,7-diphenylcubane, 7, resulted in the formation of benzoic acid.The X-ray structure of 7 shows a short phenyl-cubane bond length of 1.484 Angstroem, and the C1-C2 bond, the cubane bond between the two substituents, is substantially longer than in an unsubstituted cubane (1.607 vs. 1.558 Angstroem).The selective functionalization of either the phenyl or the cubane moiety and the synthesis of 1,4-diphenylcubane-2,7-dicarboxylic acid, 8, via oxidation of the (diisopropylamino)methyl group under mild conditions, were achieved.