# Supplementary Material (ESI) for Chemical Communications
# This journal is (c) The Royal Society of Chemistry 2009


data_global
_journal_name_full               Chem.Commun.

_journal_coden_Cambridge         0182

_publ_contact_author_name        'Feng-Ling Qing'
_publ_contact_author_email       FLQ@MAIL.SIOC.AC.CN

_publ_section_title              
;
Stereoselective Reformatskii-Claisen rearrangement:
synthesis of 2,3-Dideoxy-6,6- difluoro-2-thionucleosides
;
loop_
_publ_author_name
'Feng-Ling Qing'
'Xingang Zhang'
'Feng Zheng'

# Attachment 'cd28379.cif'

data_cd28379
_database_code_depnum_ccdc_archive 'CCDC 706937'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C9 H9 F3 N2 O3 S'
_chemical_formula_weight         282.24

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   P2(1)

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y+1/2, -z'

_cell_length_a                   6.9183(6)
_cell_length_b                   9.8313(9)
_cell_length_c                   8.2669(8)
_cell_angle_alpha                90.00
_cell_angle_beta                 100.809(2)
_cell_angle_gamma                90.00
_cell_volume                     552.30(9)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    2689
_cell_measurement_theta_min      5.016
_cell_measurement_theta_max      56.297

_exptl_crystal_description       prismatic
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.408
_exptl_crystal_size_mid          0.344
_exptl_crystal_size_min          0.257
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.697
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             288
_exptl_absorpt_coefficient_mu    0.338
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.7303
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            3279
_diffrn_reflns_av_R_equivalents  0.0477
_diffrn_reflns_av_sigmaI/netI    0.0377
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_theta_min         2.51
_diffrn_reflns_theta_max         27.00
_reflns_number_total             2191
_reflns_number_gt                2144
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SHELXTL'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.0677P)^2^+0.0475P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.033(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.05(8)
_chemical_absolute_configuration ad
_refine_ls_number_reflns         2191
_refine_ls_number_parameters     172
_refine_ls_number_restraints     3
_refine_ls_R_factor_all          0.0349
_refine_ls_R_factor_gt           0.0344
_refine_ls_wR_factor_ref         0.0962
_refine_ls_wR_factor_gt          0.0955
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_restrained_S_all      1.041
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
S1 S 0.50720(8) 1.02297(7) 0.42212(7) 0.05153(19) Uani 1 1 d . . .
F1 F 0.2579(2) 1.15096(15) 0.65674(16) 0.0539(4) Uani 1 1 d . . .
F2 F 0.01477(17) 1.0115(2) 0.57721(14) 0.0553(4) Uani 1 1 d . . .
F3 F 0.1139(2) 0.61733(14) 0.12736(17) 0.0542(4) Uani 1 1 d . . .
O1 O 0.4518(3) 0.99532(19) 0.9426(2) 0.0547(5) Uani 1 1 d D . .
O2 O -0.1144(2) 1.12054(16) 0.2365(2) 0.0459(4) Uani 1 1 d . . .
O3 O -0.2453(2) 0.71742(17) -0.0270(2) 0.0488(4) Uani 1 1 d . . .
N1 N 0.1230(2) 0.95712(17) 0.28449(19) 0.0331(3) Uani 1 1 d . . .
N2 N -0.1757(3) 0.91749(18) 0.1081(2) 0.0357(4) Uani 1 1 d D . .
C1 C 0.5340(3) 0.9315(3) 0.6184(3) 0.0496(5) Uani 1 1 d . . .
H1A H 0.5939 0.8433 0.6093 0.060 Uiso 1 1 calc R . .
H1B H 0.6178 0.9826 0.7046 0.060 Uiso 1 1 calc R . .
C2 C 0.3311(3) 0.9140(2) 0.6599(3) 0.0377(4) Uani 1 1 d . . .
H2 H 0.2758 0.8299 0.6067 0.045 Uiso 1 1 calc R . .
C3 C 0.2086(3) 1.0300(2) 0.5766(2) 0.0373(4) Uani 1 1 d . . .
C4 C 0.2464(3) 1.0486(2) 0.4012(2) 0.0358(4) Uani 1 1 d . . .
H4 H 0.2155 1.1427 0.3669 0.043 Uiso 1 1 calc R . .
C5 C -0.0599(3) 1.0077(2) 0.2123(2) 0.0332(4) Uani 1 1 d . . .
C6 C -0.1307(3) 0.7878(2) 0.0698(2) 0.0356(4) Uani 1 1 d . . .
C7 C 0.0607(3) 0.7453(2) 0.1544(2) 0.0365(4) Uani 1 1 d . . .
C8 C 0.1807(3) 0.8268(2) 0.2555(2) 0.0361(4) Uani 1 1 d . . .
H8 H 0.3039 0.7956 0.3069 0.043 Uiso 1 1 calc R . .
C9 C 0.3300(4) 0.8995(3) 0.8443(3) 0.0491(5) Uani 1 1 d . . .
H9A H 0.1962 0.9101 0.8621 0.059 Uiso 1 1 calc R . .
H9B H 0.3735 0.8086 0.8793 0.059 Uiso 1 1 calc R . .
H1 H 0.394(4) 1.065(2) 0.960(4) 0.049(8) Uiso 1 1 d D . .
H2A H -0.289(3) 0.950(3) 0.061(3) 0.039(6) Uiso 1 1 d D . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
S1 0.0338(3) 0.0649(4) 0.0575(3) -0.0058(3) 0.0129(2) -0.0101(2)
F1 0.0696(9) 0.0433(7) 0.0442(7) -0.0137(6) -0.0012(6) 0.0130(6)
F2 0.0317(6) 0.0930(12) 0.0416(6) 0.0036(7) 0.0080(5) 0.0072(7)
F3 0.0717(9) 0.0391(8) 0.0481(7) -0.0103(6) 0.0014(6) 0.0163(6)
O1 0.0513(9) 0.0538(11) 0.0488(8) -0.0135(8) -0.0165(7) 0.0148(7)
O2 0.0486(8) 0.0385(8) 0.0480(8) -0.0015(6) 0.0021(6) 0.0105(6)
O3 0.0546(10) 0.0434(9) 0.0433(8) -0.0024(7) -0.0038(7) -0.0105(7)
N1 0.0344(8) 0.0317(8) 0.0322(7) -0.0027(6) 0.0036(6) 0.0010(6)
N2 0.0342(8) 0.0359(8) 0.0344(8) 0.0041(7) -0.0004(6) 0.0019(6)
C1 0.0368(11) 0.0518(14) 0.0568(13) -0.0027(10) -0.0001(9) 0.0090(9)
C2 0.0340(9) 0.0347(10) 0.0407(10) -0.0040(8) -0.0023(8) -0.0011(7)
C3 0.0309(8) 0.0435(11) 0.0366(9) -0.0059(9) 0.0034(7) 0.0041(8)
C4 0.0349(8) 0.0338(10) 0.0377(9) -0.0039(8) 0.0042(7) -0.0019(7)
C5 0.0366(8) 0.0332(10) 0.0298(7) 0.0023(7) 0.0057(6) 0.0024(8)
C6 0.0441(10) 0.0354(10) 0.0274(8) 0.0043(7) 0.0066(7) -0.0044(7)
C7 0.0479(11) 0.0300(10) 0.0315(8) 0.0000(7) 0.0069(7) 0.0040(8)
C8 0.0367(9) 0.0403(10) 0.0310(9) 0.0002(8) 0.0053(7) 0.0092(8)
C9 0.0497(12) 0.0505(13) 0.0420(11) 0.0049(10) -0.0043(9) 0.0006(10)

_geom_special_details            
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
S1 C4 1.798(2) . ?
S1 C1 1.834(3) . ?
F1 C3 1.373(3) . ?
F2 C3 1.354(2) . ?
F3 C7 1.341(2) . ?
O1 C9 1.414(3) . ?
O1 H1 0.817(18) . ?
O2 C5 1.200(3) . ?
O3 C6 1.228(2) . ?
N1 C8 1.376(3) . ?
N1 C5 1.386(2) . ?
N1 C4 1.469(2) . ?
N2 C6 1.364(3) . ?
N2 C5 1.383(3) . ?
N2 H2A 0.869(17) . ?
C1 C2 1.516(3) . ?
C1 H1A 0.9700 . ?
C1 H1B 0.9700 . ?
C2 C3 1.508(3) . ?
C2 C9 1.532(3) . ?
C2 H2 0.9800 . ?
C3 C4 1.532(3) . ?
C4 H4 0.9800 . ?
C6 C7 1.439(3) . ?
C7 C8 1.330(3) . ?
C8 H8 0.9300 . ?
C9 H9A 0.9700 . ?
C9 H9B 0.9700 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C4 S1 C1 94.99(10) . . ?
C9 O1 H1 113(2) . . ?
C8 N1 C5 122.04(17) . . ?
C8 N1 C4 122.15(17) . . ?
C5 N1 C4 115.72(16) . . ?
C6 N2 C5 127.90(17) . . ?
C6 N2 H2A 117.8(18) . . ?
C5 N2 H2A 114.3(18) . . ?
C2 C1 S1 108.14(15) . . ?
C2 C1 H1A 110.1 . . ?
S1 C1 H1A 110.1 . . ?
C2 C1 H1B 110.1 . . ?
S1 C1 H1B 110.1 . . ?
H1A C1 H1B 108.4 . . ?
C3 C2 C1 106.03(19) . . ?
C3 C2 C9 114.70(18) . . ?
C1 C2 C9 114.40(18) . . ?
C3 C2 H2 107.1 . . ?
C1 C2 H2 107.1 . . ?
C9 C2 H2 107.1 . . ?
F2 C3 F1 105.70(16) . . ?
F2 C3 C2 111.68(19) . . ?
F1 C3 C2 111.52(15) . . ?
F2 C3 C4 111.37(14) . . ?
F1 C3 C4 106.40(17) . . ?
C2 C3 C4 109.98(16) . . ?
N1 C4 C3 111.55(16) . . ?
N1 C4 S1 115.25(13) . . ?
C3 C4 S1 103.80(13) . . ?
N1 C4 H4 108.7 . . ?
C3 C4 H4 108.7 . . ?
S1 C4 H4 108.7 . . ?
O2 C5 N2 122.26(17) . . ?
O2 C5 N1 123.35(18) . . ?
N2 C5 N1 114.39(17) . . ?
O3 C6 N2 122.06(19) . . ?
O3 C6 C7 125.1(2) . . ?
N2 C6 C7 112.81(17) . . ?
C8 C7 F3 120.76(19) . . ?
C8 C7 C6 122.64(19) . . ?
F3 C7 C6 116.60(18) . . ?
C7 C8 N1 120.20(18) . . ?
C7 C8 H8 119.9 . . ?
N1 C8 H8 119.9 . . ?
O1 C9 C2 113.4(2) . . ?
O1 C9 H9A 108.9 . . ?
C2 C9 H9A 108.9 . . ?
O1 C9 H9B 108.9 . . ?
C2 C9 H9B 108.9 . . ?
H9A C9 H9B 107.7 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C4 S1 C1 C2 3.70(18) . . . . ?
S1 C1 C2 C3 -26.7(2) . . . . ?
S1 C1 C2 C9 -154.12(17) . . . . ?
C1 C2 C3 F2 168.01(17) . . . . ?
C9 C2 C3 F2 -64.7(2) . . . . ?
C1 C2 C3 F1 -74.0(2) . . . . ?
C9 C2 C3 F1 53.3(2) . . . . ?
C1 C2 C3 C4 43.8(2) . . . . ?
C9 C2 C3 C4 171.06(17) . . . . ?
C8 N1 C4 C3 -87.4(2) . . . . ?
C5 N1 C4 C3 89.1(2) . . . . ?
C8 N1 C4 S1 30.6(2) . . . . ?
C5 N1 C4 S1 -152.87(14) . . . . ?
F2 C3 C4 N1 -39.6(2) . . . . ?
F1 C3 C4 N1 -154.35(16) . . . . ?
C2 C3 C4 N1 84.73(19) . . . . ?
F2 C3 C4 S1 -164.34(16) . . . . ?
F1 C3 C4 S1 80.94(15) . . . . ?
C2 C3 C4 S1 -39.97(19) . . . . ?
C1 S1 C4 N1 -102.43(16) . . . . ?
C1 S1 C4 C3 19.85(16) . . . . ?
C6 N2 C5 O2 179.59(19) . . . . ?
C6 N2 C5 N1 0.0(3) . . . . ?
C8 N1 C5 O2 179.36(19) . . . . ?
C4 N1 C5 O2 2.8(3) . . . . ?
C8 N1 C5 N2 -1.0(3) . . . . ?
C4 N1 C5 N2 -177.57(15) . . . . ?
C5 N2 C6 O3 -178.96(19) . . . . ?
C5 N2 C6 C7 1.2(3) . . . . ?
O3 C6 C7 C8 178.6(2) . . . . ?
N2 C6 C7 C8 -1.6(3) . . . . ?
O3 C6 C7 F3 -1.8(3) . . . . ?
N2 C6 C7 F3 178.00(17) . . . . ?
F3 C7 C8 N1 -178.85(17) . . . . ?
C6 C7 C8 N1 0.7(3) . . . . ?
C5 N1 C8 C7 0.7(3) . . . . ?
C4 N1 C8 C7 177.00(18) . . . . ?
C3 C2 C9 O1 -77.3(2) . . . . ?
C1 C2 C9 O1 45.5(3) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O1 H1 O3 0.817(18) 1.957(18) 2.769(2) 172(3) 2_556
N2 H2A O1 0.869(17) 1.927(17) 2.789(2) 171(3) 1_454

_diffrn_measured_fraction_theta_max 0.991
_diffrn_reflns_theta_full        27.00
_diffrn_measured_fraction_theta_full 0.991
_refine_diff_density_max         0.207
_refine_diff_density_min         -0.206
_refine_diff_density_rms         0.049