Abstract: 1080 M . O D A C H O W SK I , A . B O NE T, S . E S S A F I , P . C O N T I R A M S D E N, J . N . H A R V E Y, * D . L E O N O R I , * V . K . A G G A R W A L* ( U N I V E R SI T Y O F B R I S T O L A N D UN I V E R S I T Y O F M A N C HE S T E R, U K ) Development of Enantiospecific Coupling of Secondary and Tertiary Boronic Esters with Aromatic Compounds J. Am. Chem. Soc. 2016, 138, 9521–9532.

Abstract: Significance: The authors report the catalyzed nucleophilic difluoromethylation of enolizable ketones with the pentaorganosilicate Me3SiCF2H. The substrate scope includes several aromatic and aliphatic ketones and aldehydes, phthalimide, and phthalide. Comment: Me3SiCF2H is activated with an alkalimetal salt (CsF or t-BuOCs) and 18-crown-6 in catalytic amounts. [(18-crown-6)Cs]+ is essential for the stabilization of the intermediate [Me3Si(CF2H)2] – and for improving its nucleophilicity. Me3SiCF2H O R2 R1 1. CsF/18-crown-6, DME r.t., overnight 2. TBAF, r.t., 1 h 3. HCl, r.t., 1 h OH R2 R1 CF2H

Abstract: Significance: Reported is a copper-catalyzed synthesis of quinazolinones 3 by the reaction of 2amino-N-phenylbenzamides 1 with tertiary amines 2. The reaction was optimized in terms of the copper source and ligands. In general, the reaction appeared to be unaffected by the copper source, but was dependent on the ligand, as addition of phosphorus ligands led to improved yields. Of the various amines tested, acyclic amines were superior to cyclic amines in terms of yields. Compound 1 (R2 = EWG or EDG) were well tolerated. Compounds 3b and 3c were isolated in lower yields of 32% and 48%, respectively, for N-alkyl amides. The maximum scale of reaction tested was 1 mmol (212 mg) of 1a (R1 = H, R2 = Ph) with Et3N, which gave 3a in 91% yield. The reaction of 2(aminomethyl)aniline with Et3N gave 2-methylquinazoline (3d) in 12% yield. Comment: The quinazolinone skeleton is present in various alkaloids with biological activities (see first Review below), and various methods for their synthesis are known (see second Review below). This report describes an interesting way to release aldehydes from tertiary amines 2 to form Schiff bases of 1 in situ; this is followed by intramolecular addition of amidic NH on to the imine and oxidation in the presence of DDQ to afford quinazolinones 3. In the introduction to this paper, structures of pharmaceutically relevant quinazolinones are displayed, but no attempt was made to synthesize them. Since no amines 2 with R5 = Ph were tested, it is not clear whether the reaction is limited to compounds where R5 = alkyl.

Abstract: Significance: Chiral α-aminophosphonic acids are prevalent structural motifs in many biologically active molecules. The authors describe a palladium-catalyzed asymmetric hydrogenation of α-iminophosphonates to give the corresponding α-aminophosphonates enantioselectively. Comment: A series of linear and cyclic α-iminophosphonates were hydrogenated to give the corresponding optically active α-aminophosphonates in high yields and excellent enantioselectivities. The 4-methylbenzenesulfonyl group was easily removed by treatment with methanesulfonic acid, without a significant loss of enantioselectivity. Pd(OCOCF3)2 (2.0 mol%) (R )-DifluorPhos (2.4 mol%) H2 (600 psi) TFE–CH2Cl2 (2:1), 4 Å MS 40 °C, 24 h

Abstract: The hydrogenation of unsaturated compounds is a key technology in the chemical industry. The efficient catalytic reduction of water for generation of hydrogen is one of the most challenging transformations in chemistry. We continuously investigated the potential application of iron (commercial iron powder) to activate water as a terminal hydrogen source without any stoichiometric acid or base. Here in we are pleased to disclose the external-pressure-free and mild reaction protocol for reduction of alkenes using a cheap, non-hazardous, abundant, and eco-friendly “water/iron” pair as a hydrogen donor in the presence of a Pd/C catalyst (2.5 mol % w.r.t. substrate). Pd/C-catalyzed hydrogenation of olefins by using water as a hydrogen source in the presence of iron powder gave the corresponding reduction products in ≤ 96% yield (GC Yield). The formation of Fe3O4 as a byproduct was confirmed by XRD analysis.