92850-03-8

Upstream product

• 35275-62-8 1-chloroindane 
• 62-53-3 aniline 
• 496-11-7 INDANE 
• 20666-88-0 phenyl-peroxycarbamic acid tert-butyl ester 
• 95-13-6 1-indene 
• 83-33-0 inden-1-one 

Downstream Products

• 102557-75-5 indan-1-yl-phenyl-carbamic acid-(2-pyrrolidino-ethyl ester) 
• 102886-52-2 indan-1-yl-phenyl-carbamic acid-(2-piperidino-ethyl ester) 
• 119074-86-1 1-[2-(indan-1-yl-phenyl-carbamoyloxy)-ethyl]-1-methyl-pyrrolidinium; bromide 

Relevant academic research and scientific papers

Direct measurement of the thermodynamics of vinylarene hydroamination

The thermodynamics for intermolecular hydroamination of vinylarenes with arylamines have been measured directly by conducting the addition processes, as well as cleavage of the addition products, under conditions in which amine, vinylarene, and phenethylamine are all present. The reaction of N-methylaniline with styrene is exothermic by about 10 kcal/mol but nearly thermoneutral in free energy. The free energies for additions of various primary arylamines to styrene and for additions of primary arylamines to indene, dihydronaphthalene, and two vinylarenes range from 1.3 to -3.5 kcal/mol (K = 0.16-155 M-1). The steric properties of the nucleophile significantly influenced the equilibrium constant for addition, but the electronic properties of the nucleophile had a minor effect on this equilibrium constant. These measurements have led to the first successful intermolecular addition of aniline to indene and 1,2-dihydronaphthalene and shed light on factors requiring consideration when choosing substrates and reaction conditions for this transformation. Copyright

Aluminum Hydroxide Secondary Building Units in a Metal-Organic Framework Support Earth-Abundant Metal Catalysts for Broad-Scope Organic Transformations

The intrinsic heterogeneity of alumina (Al2O3) surface presents a challenge for the development of alumina-supported single-site heterogeneous catalysts and hinders the characterization of catalytic species at the molecular level as well as the elucidation of mechanistic details of the catalytic reactions. Here we report the use of aluminum hydroxide secondary building units (SBUs) in the MIL-53(Al) metal-organic framework (MOF) with the formula Al(μ2-OH)(BDC) (BDC = 1,4-benzenedicarboxylate) as a uniform and structurally defined functional mimic of Al2O3 surface for supporting Earth-abundant metal (EAM) catalysts. The μ2-OH groups in MIL-53(Al) SBUs were readily deprotonated and metalated with CoCl2 and FeCl2 to afford MIL-53(Al)-CoCl and MIL-53(Al)-FeCl precatalysts which were characterized by powder X-ray diffraction, nitrogen sorption, elemental analysis, density functional theory, and extended X-ray fine structure spectroscopy. Activation with NaBEt3H converted MIL-53(Al)-CoCl to MIL-53(Al)-CoH which effectively catalyzed hydroboration of alkynes and nitriles and hydrosilylation of esters. X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy (XANES) indicated the presence of AlIII and CoII centers in MIL-53(Al)-CoH while deuterium labeling studies suggested σ-bond metathesis as a key step for the MIL-53(Al)-CoH-catalyzed addition reactions. MIL-53(Al)-FeCl competently catalyzed oxidative Csp3-H amination and Wacker-type alkene oxidation. XANES analysis revealed the oxidation of FeII to FeIII centers in the activated MIL-53(Al)-FeCl catalyst and suggested that oxidative Csp3-H amination occurs via the formation of FeIII-OtBu species by single electron transfer between FeII centers in MIL-53(Al)-FeCl and (tBuO)2 with concomitant generation of 1 equiv of tBuO· radical, C-H activation through hydrogen atom abstraction to generate alkyl radicals, protonation of FeIII-OtBu by aniline to generate MIL-53(Al)-FeIII-anilide, and finally C-N coupling between the FeIII-anilide and alkyl radical to form the Csp3-H amination product and regenerate the FeII catalyst. These highly active single-site MOF-based solid catalysts were readily recovered and reused up to five times without significant decrease in catalytic activity. This work thus demonstrates the great potential of using the aluminum hydroxide SBUs in MOFs to support EAM catalysts for important organic transformations.

Copper-catalyzed reductive amination of aromatic and aliphatic ketones with anilines using environmental-friendly molecular hydrogen

A convenient and practical copper-catalyzed reductive amination was discovered. In the presence of easily available and inexpensive Cu(OAc) 2 various ketones react with anilines and molecular hydrogen to give the desired amines in high yields.

Benzylic and allylic amination

N-(p-Toluenesulfonyl)amino group can be directly introduced at allylic or benzylic carbon by treating alkenes or alkylarenes with t-butyl N-(p-toluenesulfonyl)peroxycarbamate in the presence of Cu(II) triflate.