Asymmetric Synthesis of 3,4-Disubstituted 2-(Trifluoromethyl)pyrrolidines through Rearrangement of Chiral 2-(2,2,2-Trifluoro-1-hydroxyethyl)azetidines.
Dolfen, Jeroen; Boydas, Esma Birsen; Van Speybroeck, Veronique; Catak, Saron; Van Hecke, Kristof; D'hooghe, Matthias; The Journal of organic chemistry 82 (2017) 10092–10109; doi:10.1021/acs.joc.7b01241

data_4032851
_publ_section_title
;
 Asymmetric Synthesis of 3,4-Disubstituted 2-(Trifluoromethyl)pyrrolidines
 through Rearrangement of Chiral
 2-(2,2,2-Trifluoro-1-hydroxyethyl)azetidines.
;
_journal_issue                   19
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              10092
_journal_page_last               10109
_journal_paper_doi               10.1021/acs.joc.7b01241
_journal_volume                  82
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C14 H16 F3 N O3'
_chemical_formula_sum            'C14 H16 F3 N O3'
_chemical_formula_weight         303.28
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-05-26
_audit_creation_method
;
Olex2 1.2
(compiled Feb 16 2016 13:09:46 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.240(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.9265(3)
_cell_length_b                   11.8003(6)
_cell_length_c                   10.0928(6)
_cell_measurement_reflns_used    3315
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      75.1520
_cell_measurement_theta_min      4.4080
_cell_volume                     698.55(7)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4839
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.962
_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   -116.00 -17.00   1.00    1.00    --  -41.55 -39.00-141.00   99
  2  \w    -66.00  33.00   1.00    1.00    --  -41.55  39.00  13.00   99
  3  \w    -33.00  66.00   1.00    1.00    --   41.55 -39.00-141.00   99
  4  \w     17.00 116.00   1.00    1.00    --   41.55  39.00  13.00   99
  5  \w     86.00 178.00   1.00    4.00    --  110.38  39.00  13.00   92
  6  \w     36.00 135.00   1.00    4.00    --  110.38 -39.00-141.00   99
  7  \w    -96.00  -2.00   1.00    1.00    --  -41.55 125.00-180.00   94
  8  \w     23.00  98.00   1.00    1.00    --   41.55-125.00  90.00   75
  9  \w     37.00 136.00   1.00    4.00    --  110.38 -45.00 120.00   99
 10  \w     37.00 121.00   1.00    4.00    --  110.38-125.00  60.00   84
 11  \w     94.00 178.00   1.00    4.00    --  110.38 125.00 -90.00   84
 12  \w     28.00 109.00   1.00    4.00    --  110.38 -94.00-120.00   81
 13  \w     37.00 121.00   1.00    4.00    --  110.38-125.00-150.00   84
 14  \w   -118.00  -9.00   1.00    1.00    --  -41.55 -77.00  60.00  109
 15  \w   -114.00 -13.00   1.00    1.00    --  -41.55 -57.00 120.00  101
 16  \w   -118.00  -9.00   1.00    1.00    --  -41.55 -77.00-120.00  109
 17  \w   -118.00  -9.00   1.00    1.00    --  -41.55 -77.00 -30.00  109
 18  \w    -33.00  62.00   1.00    1.00    --   41.55 -38.00  90.00   95
 19  \w    -33.00  66.00   1.00    1.00    --   41.55 -38.00  60.00   99
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.2242026000
_diffrn_orient_matrix_UB_12      0.0283394000
_diffrn_orient_matrix_UB_13      -0.0910896000
_diffrn_orient_matrix_UB_21      0.0899051000
_diffrn_orient_matrix_UB_22      -0.0590566000
_diffrn_orient_matrix_UB_23      -0.1181620000
_diffrn_orient_matrix_UB_31      -0.1030003000
_diffrn_orient_matrix_UB_32      -0.1129611000
_diffrn_orient_matrix_UB_33      0.0390387000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0509
_diffrn_reflns_av_unetI/netI     0.0444
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            6823
_diffrn_reflns_point_group_measured_fraction_full 0.817
_diffrn_reflns_point_group_measured_fraction_max 0.768
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.949
_diffrn_reflns_theta_min         4.426
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.102
_exptl_absorpt_correction_T_max  0.963
_exptl_absorpt_correction_T_min  0.807
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.442
_exptl_crystal_description       plate
_exptl_crystal_F_000             316
_exptl_crystal_size_max          0.405
_exptl_crystal_size_mid          0.199
_exptl_crystal_size_min          0.048
_refine_diff_density_max         0.204
_refine_diff_density_min         -0.265
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Flack x determined using 644 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.06(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     193
_refine_ls_number_reflns         2254
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0497
_refine_ls_R_factor_gt           0.0436
_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^)+(0.0718P)^2^+0.0400P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1134
_refine_ls_wR_factor_ref         0.1192
_reflns_Friedel_coverage         0.520
_reflns_Friedel_fraction_full    0.615
_reflns_Friedel_fraction_max     0.553
_reflns_number_gt                2001
_reflns_number_total             2254
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b01241_si_001.cif
_cod_data_source_block           mdh024
_cod_depositor_comments
'Adding full bibliography for 4032851--4032855.cif.'
_cod_database_code               4032851
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C14 H16 F3 N O3'
_chemical_oxdiff_usercomment     JD525
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1A), C3(H3), C4(H4), C6(H6)
2.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13), C14(H14)
2.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              34918
_shelx_hkl_checksum              67754
_olex2_exptl_crystal_mounting_method 'mounted on a nylon loop'
_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 1.553
_oxdiff_exptl_absorpt_empirical_full_min 0.683