## 2 Experimental Section
### Procedure for the Preparation of N-Phosphinylamines **1**  
Triethylamine (1.35 mL, 10.5 mmol) was added to a solution of the ketone oxime (10 mmol) in anhydrous CH\({}_{2}\)Cl\({}_{2}\) (25 mL) and Et\({}_{2}\)O (50 mL) under argon and the solution was cooled to \(-\)45 \({}^{\circ}\)C. A solution of chlorodiphenylphosphine (1.87 mL, 10 mmol) in CH\({}_{2}\)Cl\({}_{2}\) (3 mL) was added dropwise over a period of 45 min. The reaction mixture was stirred at \(-\)45 \({}^{\circ}\)C for 1 hour, slowly warmed (without removing the Dewar) to room temperature, and then stirred overnight at room temperature. Insoluble salts (Et\({}_{3}\)N-HCl) were filtered off and washed with CH\({}_{2}\)Cl\({}_{2}\)/Et\({}_{2}\)O (1:1). Solvents were then evaporated under vacuum from the liquid layer and a yellow solid was obtained, to which CH\({}_{2}\)Cl\({}_{2}\)/Et\({}_{2}\)O (1:1, 40 mL) was added. The insoluble residue was filtered off and the liquid phase was concentrated under vacuum to give a solid that was purified by column chromatography (deactivated silica gel; hexane/acetone 90:10 to 30:70), giving the expected mines in 58% (for **1a**), 52% (for **1b**) and 56% (for **1c**) yields. The corresponding physical and spectroscopic data follow:  
\(N\)**-(1-Phenylethylidene)diphenylphosphinamide (1a)**[29]: pale yellow solid; mp 120-122 \({}^{\circ}\)C; IR (KBr) 3064, 1637, 1192 cm\({}^{-1}\); \({}^{1}\)H NMR (300 MHz, CDCl\({}_{3}\)) \(\delta\) 2.97 (3H, d, \(J\) = 2.0 Hz), 7.39-7.60 (9H, m), 7.92-8.04 (4H, m), 8.09 (2H, d, \(J\) = 7.2 Hz); \({}^{13}\)C NMR (75 MHz) \(\delta\) 26.5 (d, \(J\) = 12.7 Hz), 127.9, 128.2 (d, \(J\) = 12.9 Hz), 128.6, 131.1 (d, \(J\) = 3.0 Hz), 131.3 (d, \(J\) = 9.2 Hz), 132.2, 134.4 (d, \(J\) = 134.1 Hz), 139.1 (d, \(J\) = 24.8 Hz), 181.2 (d, \(J\) = 7.9 Hz); \(m\)/\(z\) 319 (M\({}^{+}\), 53%), 318 (23), 277 (12), 242 (14), 202 (11), 201 (100), 125 (28), 77 (50), 51 (21). _Appl. Sci._**2012**, \(2\)  
\(N\)**-(1-Phenylpropylidene)diphenylphosphinamide (1b)**[44]: white solid; mp 130-132 \({}^{\circ}\)C; IR (KBr) 3058, 1630, 1190 cm\({}^{-1}\); \({}^{1}\)H NMR (300 MHz, C\({}_{6}\)D\({}_{6}\)) \(\delta\) 1.06 (3H, t, \(J\) = 7.5 Hz), 3.35 (2H, q, \(J\) = 7.5 Hz), 6.99-7.14 (9H, m), 7.83-7.86 (2H, m), 8.23-8.25 (4H, m), 13.C NMR (75 MHz, C\({}_{6}\)D\({}_{6}\)) \(\delta\) 13.5, 29.0 (d, \(J\) = 11.9 Hz), 128.6 (d, \(J\) = 9.0 Hz), 128.7 (d, \(J\) = 4.8 Hz), 131.3 (d, \(J\) = 2.9 Hz), 132.1, 132.2 (d, \(J\) = 8.7 Hz), 132.4 (d, \(J\) = 9.2 Hz), 136.6 (d, \(J\) = 131.3 Hz), 138.8 (d, \(J\) = 24.3 Hz), 186.4 (d, \(J\) = 7.6 Hz); \(m\)/\(z\) 333 (M\({}^{+}\), 46%), 256 (18), 201 (100), 132 (12), 77 (52). \(N\)**-[1-(\(p\)**-Chlorophenyl)ethylidene]diphenylphosphinamide (1c)**[44]: white solid; mp 142-144 \({}^{\circ}\)C; IR (KBr) 3058, 1640, 1199 cm\({}^{-1}\); \({}^{1}\)H NMR (300 MHz, C\({}_{6}\)D\({}_{6}\)) \(\delta\) 2.62 (3H, d, \(J\) = 1.8 Hz), 7.02-7.20 (8H, m), 7.50 (2H, d, \(J\) = 8.8 Hz), 8.17-8.26 (4H, m); \({}^{13}\)C NMR (75 MHz, C\({}_{6}\)D\({}_{6}\)) \(\delta\) 22.0 (d, \(J\) = 12.5 Hz), 127.7 (d, \(J\) = 11.8 Hz), 127.8, 128.6, 130.5 (d, \(J\) = 2.9 Hz), 131.1 (d, \(J\) = 8.1 Hz), 135.3 (d, \(J\) = 131.5 Hz), 137.4 (d, \(J\) = 26.8 Hz), 137.5, 179.0 (d, \(J\) = 7.7 Hz); \(m\)/\(z\) 355 (M\({}^{+}\)+2, 11%), 353 (M\({}^{+}\), 39), 278 (21), 276 (59), 201 (100), 154 (12), 152 (38), 77 (43). _2.3. Procedure for the Asymmetric Transfer Hydrogenation of Imines 1_  
A mixture of [RuCl\({}_{2}\)(\(p\)-cymene)]\({}_{2}\) (15 mg, 0.025 mmol), ligand **L** (0.05 mmol) and \(i\)-PrOH (2 mL) was heated to 90 \({}^{\circ}\)C (oil bath temperature) for 20 minutes. During this heating period, the initially orange reaction mixture turned into a dark red colour. The reaction was then cooled to \(-\)20 \({}^{\circ}\)C, and a solution of the imine **1** (0.5 mmol) in \(i\)-PrOH (9 mL) and \(t\)-BuOK (2.5 mL of a 0.1 M solution in \(i\)-PrOH, 0.25 mmol) were successively added. The solution was stirred for 1 h at the same temperature, slowly warmed (without removing the Dewar) to room temperature (\(ca\).