[reaction: see text] The highly regioselective hydrogenolysis of bis(alpha-methylbenzyl)amine derivatives proceeded with influence not from the electronic effect but from the steric effect of the trifluoromethyl substituent on the aromatic ring to provide a practical asymmetric synthesis of trifluoromethyl-substituted alpha-phenylethylamines.

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The reactions of chlorine(I) and bromine(I) trifluoromethanesulfonates with a variety of perfluoroalkyl halides are reported. The reactions form Bra, Cla, or BrCl and the corresponding trifluoromethanesulfonate derivatives of the alkyls in good yields. Twelve new esters are reported and characterized. An Sni-type mechanism for the reactions is proposed with complete retention of configuration by the alkyl on substitution. 24-111 to 22 CCIF3 (3.5), SO3 Cl (5.0) C2F5Br (5.0) 15 -40 to -5 CF3S03C2F5 (2.9), C2F6 (0.5) BrCl (5.9) Cl (6.5) C3F7Br (6.5) 36 -40 to 22 CF3S03C3F7 (4.2), C3F8 (0.6) BrCl (5.7) Cl (4.6) CC12F2 (5.1) 15 -78 to 22 CF3S03CF2C1 (4.2), Cl2 (4.5) 0(5.1) CBr2F2 (5.4) 1 -111 CF3S03CF2Br (0.8), COF2 (4.0), (CF3S02)20 (2.0), BrCl Cl (3.3) CBr2F2 (4.5) 1 -160* ^CF3SG3CF2Br (2.0), COF2 (1.2), (CF3S02)2G (0.6), BrCl Cl(5.0) CCI3F (7.0) 15 -78 to 22 CF3S03CFC12 (4.4), (CF3S02)2G (0.2) Br (3.9) CF3Br (5.0) 15 -111 to -10 CF3S03CF3 (2.9), Br2 (3.9) Br (2.0) CFCb (5.0) 15 -78 to 22 CF3S03CFC12 (1.0), BrCl Cl (4.4) CC12F2 (2.0) 15 -60 to 22 (CF3S03)2CF2 (0.1), CF3S03CF2C1 (1.0), COF2 (0.8), (CF3S02)20 (0.8), Cl2 0(1.2) CBr2F2 (2.5) 11 -150 to -130» COF2 (1.9), (CF3S02)20 (1.5), BrCl Cl (6.1) CC13F (3.0) 15 -85 to -40 CF3S03CC12F (2.2), (CF3SG2) O (0.7), COC1F, Cl2 Br (5.0) CBr2F2 (2.4) 24 -111 to -60 (CF3S03)2CF2 (0.7), CF3S03CF2Br (0.7), (CF3S02)2G (0.35), Br2 (4.5), COF2 (0.9), CF3S03CF3 (0.4) Br (4.1) CC12F2 (2.0) 15 -111 to-50 (CF3S03)2CF2 (0.12), CF3S03CF2C1 (0.6), (CF3SG2)20 (0.6), COF2 (1.), cf3so3cf3 (0.7), BrCl (2.2) Cl (3.5) (CF2Br)2 (1.6) 15 -88 to -30 (CF3S03CF2)2 (0.52), CF3S03CF2CF2Br (0.99), C2F5Br (0.1), BrCl (3.6) 0(5.6) (CF2Br)2 (2.7) 15 -111 to 22* CF3SG3CF2CF2Br (1.0), CF3S03CF2C1(2.9), C2F5Br (1.5), BrCl-Cl2 (5.4) Cl (6.0) (CF2Br)2 (3.0) 1 -111 to-88CF3S03CF2CF2Br (1.7), CF3S03CF3 (0.8), C2F5Br (0.4), BrCl (3.2) Cl (6.9) CBr3F (2.3) 15 -111* CF3S03C(0)F (1.6), (CF3S02)20 (1.8), BrCl (1.6), COBrF Cl (6.9) CC13F (2.3) 24