Synthesis of (2S)-2-Chloro-2-fluororibolactone via Stereoselective Electrophilic Fluorination.
De Schutter, Coralie; Sari, Ozkan; Coats, Steven J.; Amblard, Franck; Schinazi, Raymond F.; The Journal of organic chemistry 82 (2017) 13171–13178; doi:10.1021/acs.joc.7b02245

data_4033242
_publ_section_title
;
 Synthesis of (2S)-2-Chloro-2-fluororibolactone via Stereoselective
 Electrophilic Fluorination.
;
_journal_issue                   24
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              13171
_journal_page_last               13178
_journal_paper_doi               10.1021/acs.joc.7b02245
_journal_volume                  82
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H23 Cl F N O7 Si'
_chemical_formula_sum            'C18 H23 Cl F N O7 Si'
_chemical_formula_weight         447.91
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-09-12
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2017.07.20 svn.r3457 for OlexSys, GUI svn.r5370)
;
_cell_angle_alpha                82.254(8)
_cell_angle_beta                 84.013(8)
_cell_angle_gamma                63.460(10)
_cell_formula_units_Z            1
_cell_length_a                   6.5977(7)
_cell_length_b                   6.9540(7)
_cell_length_c                   13.0578(13)
_cell_measurement_reflns_used    4188
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.5310
_cell_measurement_theta_min      1.5520
_cell_volume                     530.42(10)
_computing_cell_refinement       'CrysAlisPro 1.171.39.9g (Rigaku OD, 2015)'
_computing_data_collection       'APEX2 v2016.5-1 (Bruker, 2014)'
_computing_data_reduction        'CrysAlisPro 1.171.39.9g (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.956
_diffrn_measured_fraction_theta_max 0.956
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -12.69 195.31   1.00   30.00    --   27.07  73.80  54.24  208
  2  \w    -12.69 195.31   1.00   30.00    --   27.07  73.80-105.76  208
  3  \w    -12.69 195.31   1.00   30.00    --   27.07  73.80 -25.76  208
  4  \w    -12.69 195.31   1.00   30.00    --   27.07  73.80 174.24  208
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE diffractometer'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0945482000
_diffrn_orient_matrix_UB_12      0.0362262000
_diffrn_orient_matrix_UB_13      -0.0311654000
_diffrn_orient_matrix_UB_21      0.0589872000
_diffrn_orient_matrix_UB_22      0.0346621000
_diffrn_orient_matrix_UB_23      -0.0411112000
_diffrn_orient_matrix_UB_31      0.0453626000
_diffrn_orient_matrix_UB_32      -0.1030260000
_diffrn_orient_matrix_UB_33      -0.0187408000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0270
_diffrn_reflns_av_unetI/netI     0.0383
_diffrn_reflns_Laue_measured_fraction_full 0.956
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            5276
_diffrn_reflns_point_group_measured_fraction_full 0.892
_diffrn_reflns_point_group_measured_fraction_max 0.892
_diffrn_reflns_theta_full        24.711
_diffrn_reflns_theta_max         24.711
_diffrn_reflns_theta_min         1.576
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_current           35
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_diffrn_source_voltage           45
_exptl_absorpt_coefficient_mu    0.284
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62947
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro 1.171.39.9g (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.402
_exptl_crystal_description       plate
_exptl_crystal_F_000             234
_exptl_crystal_recrystallization_method
'Slow evaporation from diethyl ether and pentane.'
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.456
_refine_diff_density_min         -0.257
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Flack x determined using 1275 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     267
_refine_ls_number_reflns         3229
_refine_ls_number_restraints     165
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0474
_refine_ls_R_factor_gt           0.0429
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0532P)^2^+0.4575P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1000
_refine_ls_wR_factor_ref         0.1022
_reflns_Friedel_coverage         0.868
_reflns_Friedel_fraction_full    0.829
_reflns_Friedel_fraction_max     0.829
_reflns_number_gt                3010
_reflns_number_total             3229
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b02245_si_003.cif
_cod_data_source_block           cds3-023bf1
_cod_depositor_comments
'Adding full bibliography for 4033242--4033243.cif.'
_cod_database_code               4033242
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C18H23ClFNO7Si
_reflns_odcompleteness_completeness 95.17
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.63
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C2) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C4) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C16) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
3. Rigid body (RIGU) restrains
 F1, C3, Cl1, C2, C4
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O3, C2, C1, C3
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C3, C4
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C3, C4, O1, O2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C13, C14, C15, C16, N1, O6, O7, C17, C18, C6, O4, O5
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4.a Ternary CH refined with riding coordinates:
 C2(H2), C1(H1)
4.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B)
4.c Aromatic/amide H refined with riding coordinates:
 C17(H17), C15(H15), C18(H18), C14(H14)
4.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C8(H8A,H8B,H8C), C7(H7A,H7B,H7C), C10(H10A,H10B,H10C),
 C12(H12A,H12B,H12C)
;
_shelx_res_checksum              63524
_shelx_hkl_checksum              62084
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_original_sample_id cds3-023bF1
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.497
_oxdiff_exptl_absorpt_empirical_full_min 0.781