Synthesis of Tetra-ortho-Substituted, Phosphorus- Containing and Carbonyl-Containing Biaryls Utilizing a Diels-Alder Approach

Transcription

1 Synthesis of Tetra-ortho-Substituted, Phosphorus- Containing and Carbonyl-Containing Biaryls Utilizing a Diels-Alder Approach Bradley O. Ashburn and Rich G. Carter* and Lev N. Zakharov Department of Chemistry, Oregon State University, Corvallis, OR Electronic Supplementary Information: X-ray Crystallographic Data

2 X-ray Crystal Structure Determination. X-ray diffraction intensity data were collected with a Bruker Smart Apex CCD diffractometer at 153(2) K (5b, 14a, 14c, 28a, 28e, 28f), 173(2) K (34, 57) and 123 K (47b, 54aS) using MoKa - radiation ( Å). Crystallographic data and some details of data collections and refinements for the investigated structures are given in Table 1. The structure was solved using direct methods, completed by subsequent difference Fourier syntheses, and refined by full matrix least-squares procedures on F 2. The non-hydrogen atoms in all structures were refined with anisotropic thermal parameters except those in a disordered CH 2 CH 3 group in 5b which were refined with isotropic thermal parameters. H atoms in 5b, 14a, 28a, 28e and 57 were found from the F-maps and refined with isotropic thermal parameters. In the structures of 14c, 28f, 34, 54aS H atoms were treated in calculated positions and refined in a rigid group model. The halogen atoms and NO 2 groups in 5b, 14c and 47b are disordered over two positions related to two opposite orientations of Ph-rings; the ratio Hal:NO 2 is 50:50 (5b), 66:34 (14c) and 91:09 (47b). The CH 2 CH 3 group in 5b, - OCH 3 group in 14c and -C 6 H 10 group in 28f are disordered over two positions as well. Only one position of these groups is shown on Figures. Highly disordered solvent molecules in 28e, 28f and 34 were treated by SQUEEZE (Van der Sluis, P. & Spek, A. L. (1990) Acta Cryst., Sect. A, A46, ). Corrections of the X-ray data by SQUEEZE were close to required values: respectively, 117 vs. 100 electron/cell for cyclohexane, C 6 H 14, solvent molecules in 28e disordered around an inversion centers; 362 vs. 384 electron/cell for ethyl acetate, CH 3 COOC 2 H 5, solvent molecules in 28f disordered around a two-fold axis; and 196 vs. 192 electron/cell for two symmetrically independent ethyl acetate, CH 3 COOC 2 H 5, solvent molecules in 34 disordered in general positions. An absolute structure of 54aS was determined based on known absolute configuration of the initial product. All software and scattering factor sources are contained in the SHELXTL (5.10) program package (G.Sheldrick, Bruker XRD, Madison, WI). Table 1. Summary of Crystallographic Data and Refinement Parameters for 5b, 14a, 14c, 28a, 28e, 28f, 34, 47b, 54aS, 57. 5b(rc2) 14a(rc1) 14c(rc3) 28a (rc5) Empirical C 17 H 19 ClN 1 SO 7 C 32 H 25 BrNO 5 P C 32 H 37 BrNO 5 P C 39 H 46 NO 4 SP formula P fw temp (K) 153(2) 153(2) 153(2) 153(2) radiation (Å) cryst syst Orthorhombic Monoclinic Triclinic Monoclinic space group Pnma P2(1)/n P-1 C2/c cell constants a (Å) b (Å) c (Å) (17) (15) (10) (4) (4) (11) (6) (8) (9) (14)) (7) (10)

3 a (deg) b (deg) g (deg) V( Å 3 ) (4) (1) (19) (10) (10) (10) (16) (1) (2) Z, Z 4, 0.5 4, 1 2,1 8,1 d calcd (g/cm 3 ) abs coeff (mm -1 ) F (000) q range (deg) h,k,l ranges -20 h h h h 35 collected -147 k l k l k l k l 25 no. reflns collected [R int =0.0386] [R int =0.0263] [R int =0.0339] [R int =0.0263] no. unique reflns abs SADABS SADABS SADABS SADABS correction (T min /T max ) (0.556) (0.920) (0.786) (0.830) Refinement method Full-matrix least-squares on F 2 Full-matrix leastsquares on F 2 No. of params c GOF w Final F induces [I > 2s(I)] R indices(all R1 = R1 = data) wr2 = wr2 = a R1=å F 0 - F C /S F 0. b wr2= å F F C 2 /S w(f 0 ) 2 1/2. w =1/[(F 2 0 ) 2 +(ap) 2 +bp], where P=(F 2 0 +F 2 c )/3. Full-matrix least-squares on F 2 Full-matrix least-squares on R1 a = R1 a = R1 a = R1 a = wr2 b = wr2 b = wr2 b = wr2 b = R1 = wr2 = F 2 R1 = wr2 = Table 1 (Continued). Summary of Crystallographic Data and Refinement Parameters for 5b, 14a, 14c, 28a, 29e, 28f, 34, 47b, 54aS, e (rc7) 28f (rc6) 34 (rc12) 47b(rc13) Empirical C 43 H 53 NO 5 P C 42 H 45 F 5 NO 7 P C 42 H 53 ClNO 2 P C 16 H 14 BrNO 5 formula fw temp (K) 153(2) 153(2) 173(2) 123(2) radiation (Å) cryst syst Monoclinic Orthorhombic Triclinic Monoclinic

4 space group P2 1 /c Pnna P-1 P2 1 /c cell constants a (Å) b (Å) c (Å) a (deg) b (deg) g (deg) V( Å 3 ) (9) (7) (3) (10) (5) (12) (9) (8) (7) (3) (4) (4) (4) (4) (4) 4283(2) (19) (9) (12) (2) (3) Z, Z 4,1 8, 1 4, 2 4,1 d calcd (g/cm 3 ) abs coeff (mm -1 ) F (000) q range (deg) h,k,l ranges -13 h h h h 17 collected -10 k l k l k l k 9-14 l 15 no. reflns collected [R int =0.0438] [R int =0.0495] [R int =0.0494] [R int =0.0363] no. unique reflns abs SADABS SADABS SADABS SADABS correction (T min /T max ) (0.643) (0.787) (0.708) (0.739) Refinement method Full-matrix least-squares on F 2 Full-matrix leastsquares on F 2 No. of params c GOF w Final F induces [I > 2s(I)] R indices(all R1 = R1 = data) wr2 = wr2 = a R1=å F 0 - F C /S F 0. b wr2= å F F C 2 /S w(f 0 ) 2 1/2. w =1/[(F 2 0 ) 2 +(ap) 2 +bp], where P=(F 2 0 +F 2 c )/3. Full-matrix least-squares on F 2 Full-matrix least-squares on R1 a = R1 a = R1 a = R1 a = wr2 b = wr2 b = wr2 b = wr2 b = R1 = wr2 = F 2 R1 = wr2 = Table 1 (Continued). Summary of Crystallographic Data and Refinement Parameters for 5b, 14a, 14c, 28a, 29e, 28f, 34, 47b, 54aS, 57.

5 54aS (rc15) 57 (rc18) C 24 H 19 BrN 2 O 6 C 14 H 10 BrN 3 O 2 Empirical formula fw temp (K) 123(2) 173(2) radiation (Å) cryst syst Triclinic Monoclinic space group P1 P2 1 /n cell constants a (Å) b (Å) c (Å) a (deg) b (deg) g (deg) V( Å 3 ) (13) (13) (15) (2) (2) (2) (2) 9.788(2) (18) (3) (3) (4) Z, Z 2, 2 4, 1 d calcd (g/cm 3 ) abs coeff (mm -1 ) F (000) q range (deg) h,k,l ranges -13 h h 12 collected -13 k l k l 18 no. reflns collected [R int =0.0181] [R int =0.0244] no. unique reflns abs SADABS SADABS correction (T min /T max ) (0.755) (0.539) Refinement method No. of params c GOF w Final F induces [I > 2s I ] R indices all data Full-matrix leastsquares Full-matrix least- on F 2 squares on F R1 a = R1 a = wr2 b = wr2 b = R1 = wr2 = R1 = wr2 =

6

7

8

9

10

11

12

13

14

15

16

17