Fluorine-Containing Allenylpalladium Complexes
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(H-10′). 13C NMR (CDCl3): 120.95 q, J = 280.8 (CF3); 93.44; 67.99 d, J = 2.1 (CF3CHC);
67.64 q, J = 38.8 (CF3CH); 39.52; 31.11; 28.33; 27.66; 22.43; 18.62; 13.93. 19F NMR (CDCl3):
–77.54 d, 3 F, J = 6.6 (CF3). IR (n eat): 2 936, 2 862, 2 245, 1 466, 1 377. For C11H17F3O3S
(286.3) calculated: 46.14% C, 5.98% H; foun d: 45.75% C, 5.77% H.
(2S)-1,1,1-Trifluorodec-3-yn-2-yl methanesulfonate (1a). [α ]2D1 +71.5 (c 0.815, CHCl3, 96% ee).
All oth er data were iden tical with th ose of racem ic 1a.
1-tert-Butyldimethylsilyloxy-5,5,5-trifluoropent-2-yn-4-yl methanesulfonate (1b ). 1H NMR
(CDCl3): 5.52 q, 1 H, J(4′,F) = 5.0 (H-4′); 4.40 s, 2 H (H-1′); 3.18 s, 3 H (CH3SO3); 0.90 s, 9 H
(t-Bu); 0.11 s, 6 H (t-Bu(CH3)2Si). 13C NMR (CDCl3): 120.81 q, J = 281.0 (CF3); 90.51; 72.19;
67.13 q, J = 38.8 (CF3CH); 51.32; 39.55; 25.60; 18.14; 5.37. 19F NMR (CDCl3): –77.07 d, 3 F,
J = 6.6 (CF3). IR (n eat): 2 955, 2 936, 2 862, 2 361, 2 241, 1 474, 1 377, 1 273.
1-Benzyloxy-5,5,5-trifluoropent-2-yn-4-yl methanesulfonate (1c). 1H NMR (CDCl3): 7.30–7.38 m ,
5 H (Ph ); 5.56 tq, 1 H, J(1′,4′ an d 4′,F) = 5.5, 1.5 (H-4′); 4.59 s, 2 H (Ph CH2O); 4.25 d, 2 H,
J(1′,4′) = 1.5 (H-1′); 3.16 s, 3 H (CH3SO3). 13C NMR (CDCl3): 136.59; 128.54; 128.16; 128.14;
120.80 q, J = 281.1 (CF3); 74.02 d, J = 2.0 (CF3CHC); 72.02; 66.86 q, J = 38.8 (CF3CH); 56.70;
39.47. 19F NMR (CDCl3): –77.20 d, 3 F, J = 4.4 (CF3). IR (n eat): 3 032, 2 943, 2 866, 2 237,
1 377, 1 273. For C13H13F3O4S (322.3) calculated: 48.45% C, 4.07% H; foun d: 48.18% C,
4.02% H.
1,1,1-Trifluoro-5,5-dimethylhex-3-yn-2-yl methanesulfonate (1d ). 1H NMR (CDCl3): 6.17 d,
1 H, J(4′,5′) = 15.50 (H-4′); 5.45 dd, 1 H, J(2′,3′ an d 3′,4′) = 8.00, 15.50 (H-3′); 5.24 dq, 1 H,
J(2′,3′ an d 2′,F) = 8.00, 6.00 (H-2′); 3.07 s, 3 H (CH3SO3); 1.07 s, 9 H (t-Bu). 13C NMR
(CDCl3): 154.28; 122.35 q, J = 280.73 (CF3); 113.31; 78.21 q, J = 34.19 (CF3CH); 39.55;
33.70; 28.72.
1,1,1-Trifluoro-4-trimethylsilyl-but-3-yn-2-yl methanesulfonate (1e). 1H NMR (CDCl3): 5.47 q,
1 H, J(2′,F) = 5.0 (H-2′); 3.20 s, 3 H (CH3SO3); 0.24 s, 9 H (TMS). 13C NMR (CDCl3):
116.21 q, J = 281.1 (CF3); 98.63; 91.21; 67.41 q, J = 38.8 (CF3CH); 39.58; –0.84. 19F NMR
(CDCl3): –77.05 d, 3 F, J = 4.4 (CF3). IR (n eat): 3 036, 2 963, 1 736, 1 371.
1,1-Difluorodec-3-yn-2-yl methanesulfonate (1f). 1H NMR (CDCl3): 5.83 td, 1 H, J(1′,F an d
1′,2′) = 55.0, 2.0 (H-1′); 5.26–5.31 m , 1 H (H-2′); 3.15 s, 3 H (CH3SO3); 2.29 td, 2 H, J(5′,6′
an d 2′,5′) = 7.0, 2.0 (H-5′); 1.55 tt, 2 H, J(5′,6′ an d 6′,7′) = 7.5, 7.5 (H-6′); 1.24–1.41 m , 6 H
(H-7′, 8′, 9′); 0.89 t, J(9′,10′) = 6.5, 3 H (H-10′). 13C NMR (CDCl3): 111.56 t, J = 248.5 (CF2H);
93.34; 69.28; 69.22 t, J = 29.6 (CF2HCH); 39.34; 31.10; 28.34; 27.79; 22.40; 18.62; 13.90.
19F NMR (CDCl3): –128.43 ddd, 1 F, J = 286.2, 55.1, 8.8 (CF2H); –125.67 ddd, 1 F, J = 286.2,
55.1, 8.8 (CF2H). IR (n eat): 2 936, 2 862, 2 241, 1 466, 1 373. For C11H18F2O3S (268.3) calcu-
lated: 49.24% C, 6.76% H; foun d: 49.09% C, 6.62% H.
1,1,1,2,2-Pentafluoroundec-4-yn-3-yl methanesulfonate (1g). 1H NMR (CDCl3): 5.58 t, 1 H,
J(3′,F) = 9.0 (H-3′); 3.17 s, 3 H (CH3SO3); 2.31 td, 2 H, J(3′,6′ an d 6′,7′) = 7.0, 2.0 (H-6′);
1.55 tt, 2 H, J(6′,7′ an d 7′,8′) = 7.5, 7.5 (H-7′); 1.27–1.42 m , 6 H (H-8′, 9′, 10′); 0.89 t, 3 H,
J(10′,11′) = 7.0 (H-11′). 13C NMR (CDCl3): 118.17 qt, J = 287.1, 34.2 (CF3); 110.52 tq, J =
261.6, 37.4 (CF3CF2); 94.56; 67.50 t, J = 2.9 (CF3CF2CH); 67.25; 39.56; 31.10; 28.29; 27.63;
22.41; 18.62; 13.87. 19F NMR (CDCl3): –122.95 dd, 2 F, J = 26.4, 8.8 (CF3CF2); –81.40 s, 3 F
(CF3). IR (n eat): 2 936, 2 862, 2 245, 1 466, 1 377, 1 335. For C12H17F5O3S (336.3) calcu-
lated: 42.86% C, 5.09% H; foun d: 42.93% C, 4.96% H.
(3S)-1,1,1,2,2-Pentafluoroundec-4-yn-3-yl methanesulfonate (1g). [α ]2D1 +61.9 (c 0.825, CHCl3,
94% ee). All oth er data were iden tical with th ose of racem ic 1g.
Collect. Czech. Chem. Commun. (Vol. 67) (2002)