Enantioselective Catalytic Fluorinative Aza-semipinacol Rearrangement.
Romanov-Michailidis, Fedor; Pupier, Marion; Besnard, Céline; Bürgi, Thomas; Alexakis, Alexandre; Organic letters 16 (2014) 4988–4991; doi:10.1021/ol5022355

data_1517923
_publ_section_title
;
 Enantioselective Catalytic Fluorinative Aza-semipinacol Rearrangement.
;
_journal_issue                   19
_journal_name_full               'Organic letters'
_journal_page_first              4988
_journal_page_last               4991
_journal_paper_doi               10.1021/ol5022355
_journal_volume                  16
_journal_year                    2014
_chemical_formula_moiety         'C20 H21 Br F N O2 S'
_chemical_formula_sum            'C20 H21 Br F N O2 S'
_chemical_formula_weight         438.35
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2014-07-07
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2014.06.27 svn.r2953 for OlexSys, GUI svn.r4855)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.6948(4)
_cell_length_b                   7.70147(15)
_cell_length_c                   26.3894(6)
_cell_measurement_reflns_used    5282
_cell_measurement_temperature    180.1(6)
_cell_measurement_theta_max      72.4080
_cell_measurement_theta_min      3.3220
_cell_volume                     3799.48(14)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2013)'
_diffrn_ambient_temperature      180.1(6)
_diffrn_detector_area_resol_mean 10.4679
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_details
;
  1 omega  -62.00  -34.80   0.8000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865 -178.0000   90.0000 34

  2 omega  -98.00  -22.80   0.8000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865  -57.0000  120.0000 94

  3 omega  -67.00   39.40   0.8000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865   57.0000  -90.0000 133

  4 omega  101.00  154.60   0.8000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716  112.0000   90.0000 67

  5 omega   31.00   97.40   0.8000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716  -45.0000 -150.0000 83

  6 omega   47.00   91.00   0.8000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716  -30.0000  -90.0000 55

  7 omega   47.80   91.00   0.8000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716  -30.0000    0.0000 54

  8 omega  101.00  163.40   0.8000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716  112.0000  -60.0000 78

  9 omega   60.00   91.20   0.8000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716  -30.0000   30.0000 39

 10 omega  100.00  176.00   0.8000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716   15.0000   90.0000 95

 11 omega   51.00   79.00   0.8000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716   15.0000   90.0000 35
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0091330000
_diffrn_orient_matrix_UB_12      0.0394040000
_diffrn_orient_matrix_UB_13      0.0568712000
_diffrn_orient_matrix_UB_21      0.0623913000
_diffrn_orient_matrix_UB_22      -0.1237013000
_diffrn_orient_matrix_UB_23      0.0123558000
_diffrn_orient_matrix_UB_31      0.0530578000
_diffrn_orient_matrix_UB_32      0.1522983000
_diffrn_orient_matrix_UB_33      -0.0046572000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0233
_diffrn_reflns_av_unetI/netI     0.0221
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            11584
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.528
_diffrn_reflns_theta_min         3.350
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.182
_exptl_absorpt_correction_T_max  0.937
_exptl_absorpt_correction_T_min  0.557
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.533
_exptl_crystal_description       plate
_exptl_crystal_F_000             1792
_exptl_crystal_size_max          0.4143
_exptl_crystal_size_mid          0.1927
_exptl_crystal_size_min          0.0197
_refine_diff_density_max         0.588
_refine_diff_density_min         -0.539
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     239
_refine_ls_number_reflns         3704
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0387
_refine_ls_R_factor_gt           0.0329
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0467P)^2^+2.1721P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0858
_refine_ls_wR_factor_ref         0.0908
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3246
_reflns_number_total             3704
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5022355_si_001.cif
_cod_data_source_block           fr1319
_cod_original_cell_volume        3799.48(13)
_cod_database_code               1517923
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'Br C20 H21 F1 N1 O2'
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C5(H5), C9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C7(H7A,H7B), C12(H12A,H12B), C6(H6A,H6B)
2.c Aromatic/amide H refined with riding coordinates:
 C17(H17), C16(H16), C20(H20), C25(H25), C15(H15), C21(H21), C24(H24)
2.d Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C)
;
_olex2_submission_special_instructions 'No special instructions were received'