Phosphoric acids transfer hydrogenation with

A significant limitation in both of these attractive protocols is the requirement of stoichiometric quantities of the Hantzsch ester for the transfer hydrogenation step. Recently, Seller [318] disclosed a strategy that uses a chiral phosphoric acid in combination with Knolker s iron complex (77) and hydrogen gas to complete the reduction with good enantioselectivity (up to 94% ee) (Scheme 15.96). Because Au is used for the alkyne hydroamination step, the Markovnikov product is selectively obtained. While a variety of arylamines can be used in combination with either aryl- or alkylalkynes, alkylamine substrates continue to present a challenge [319]. 

Au(l)/Br0nsted Acid System Han et al. developed an unprecedented protocol to synthesize tetrahydroquinolines 332 directly from 2-(2-propynyl)aniline derivatives 365 in one pot under relay catalysis of an achiral Au complex 368 and a chiral phosphoric acid 5j [131]. The Au -catalyzed intramolecular hydroamination of 2-(2-propynyl)aniline provided the 1,4-dihydroquinolines 366, followed by isomerization into imine-like 3,4-dihydroquinoliniums 367 with 5j. This active intermediate then underwent asymmetric transfer hydrogenation with Hantzsch ester to produce enantioenriched tetrahydroquinoUne products (Scheme 2.97). 

Transfer the residue prepared as in Section 6.1.1 into a 300-nL separatory funnel with 25 mL of phosphate buffer solution (0.1 M, pH 7.4). Add 10 mL of saturated aqueous sodium chloride and 50 mL of 0.5 M sodium hydrogen carbonate to the funnel and shake the funnel vigorously for 1 min. Add 70 mL of ethyl acetate to wash the aqueous layer to the funnel, shake, separate, and discard the ethyl acetate layer. Repeat this extraction procedure three times. Add 2 mL of phosphoric acid and 20 mL of an acetate buffer solution (0.1 M, pH 4) to the aqueous layer and extract the mixmre with 50 mL of ethyl acetate three times. Combine the extracts and filter into a 500-mL round-bottom flask through 60 g of anhydrous sodium sulfate supported by a plug of cotton wool in a funnel. Concentrate the filtrate to dryness under reduced pressure. 

Henbest and Mitchell [78] have shown that water can be used as hydrogen source with chloroiridic acid (6) as the catalyst through oxidation of phosphorous acid (59) to phosphoric acid (60) in aqueous 2-propanol. Under these conditions, no hydrogen transfer occurs from 2-propanol. However, iridium complexes with sulfoxide or phosphine ligands show the usual transfer from 2-pro-panol [79-81]. 

A hindered BINAP-phosphoric acid catalyst allows the enantioselective reduction of ketimines via transfer hydrogenation.307 Imines can be generated in situ from either aliphatic or aromatic ketones, with low catalyst loading. 

Phosphoric acid catalysts, bearing bulky groups, have been devised for the asymmetric transfer hydrogenation of imines with Hantsch ester. With the catalyst (14), (g) enantioselectivity up to 93% has been achieved in the reduction of aromatic imines. 

A special type of pseudo-polymorphism is that related to the proton transfer along an X-H Y interaction. The motion may not be associated with a phase transition, but may well imply the transformation of a molecular crystal into a molecular salt. Wilson [34] has discussed, on the basis of an elegant neutron diffraction study, the migration of the proton along an O-H O bond in a co-crystal urea-phosphoric acid (1 1) whereby the proton migrates towards the mid-point of the hydrogen bond as the temperature is increased, becoming essentially centred at T > 300 K. Wiechert and Mootz [35] isolated two crystalline materials composed of pyridine and formic acid of different composition. In the 1 1 co-crystal the formic acid molecule retains its proton and transfer to the basic N-atom on the... 

We thought to start with the metal-free biomimetic transfer hydrogenation of a,(-)-unsaturated aldehydes as a model reaction which has been earlier discovered in our laboratory and independently in that of MacMillan et al. (Scheme 24). We have prepared a large number of ammonium salts as crystalline solids by mixing different primary and secondary amines with a chiral phosphoric acid. In particular, the ammonium salts of sterically hindered chiral phosphoric acids could catalyze... 

Kadyrov R, Riermeier TH (2003) Highly enantioselective hydrogen-transfer reductive amination catalytic asymmetric synthesis of primary amines. Angew Chem Int Ed Engl 42 5472-5474 Kang Q, Zhao ZA, You SL (2007) Highly enantioselective Friedel-Crafts reaction of indoles with imines by a chiral phosphoric acid. J Am Chem Soc 129 1484-1485... 

Solubilization, uptake, and precipitation of Ca and Si are directly (or at least energetically) linked to the photosynthetic and respiratory cycling of C, H, and O. Acids from nitrification and sulfur oxidation aid phosphorus mobilization photosynthesis or respiration is required for the uptake and conversion of phosphorous into high-energy phosphate. Sulfur is oxidized (with the concomitant reduction of nitrate) by Thiobacillus denitrificans, likewise, some extremely thermophilic methanogens can transfer hydrogen not only to CO2, but also to S. These are a few examples of interrelations involved in biogeochemical cycles. 

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