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_4032855
_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         'C25 H25 F3 N2 O'
_chemical_formula_sum            'C25 H25 F3 N2 O'
_chemical_formula_weight         426.47
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2016-06-16
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.58530(14)
_cell_length_b                   10.83863(13)
_cell_length_c                   20.3107(2)
_cell_measurement_reflns_used    15951
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      75.1400
_cell_measurement_theta_min      4.3230
_cell_volume                     2110.11(4)
_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    'olex2.solve (Bourhis et al., 2015)'
_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 1.000
_diffrn_measured_fraction_theta_max 0.992
_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    -90.00   9.00   1.00    1.00    --  -41.80 112.00 114.00   99
  2  \w    -35.00  71.00   1.00    1.00    --   41.80 -28.00-132.00  106
  3  \w    101.00 178.00   1.00    1.00    --  109.13 100.00-146.00   77
  4  \w     33.00 116.00   1.00    1.00    --  109.13-112.00  21.00   83
  5  \w     80.00 178.00   1.00    1.00    --  109.13  28.00  29.00   98
  6  \w   -118.00  -9.00   1.00    1.00    --  -41.80 -77.00  30.00  109
  7  \w     37.00 138.00   1.00    1.00    --  109.13 -61.00 -90.00  101
  8  \w     36.00 121.00   1.00    1.00    --  109.13-125.00-150.00   85
  9  \w     36.00 135.00   1.00    1.00    --  109.13 -45.00   0.00   99
 10  \w    101.00 178.00   1.00    1.00    --  109.13 112.00 114.00   77
 11  \w   -114.00 -14.00   1.00    1.00    --  -41.80 -57.00 120.00  100
 12  \w   -114.00 -14.00   1.00    1.00    --  -41.80 -57.00 -90.00  100
 13  \w   -114.00 -14.00   1.00    1.00    --  -41.80 -57.00-150.00  100
 14  \w     36.00 135.00   1.00    1.00    --  109.13 -45.00 150.00   99
 15  \w     56.00 178.00   1.00    1.00    --  109.13  15.00 -60.00  122
 16  \w     83.00 178.00   1.00    1.00    --  109.13  45.00-180.00   95
 17  \w     83.00 178.00   1.00    1.00    --  109.13  45.00  60.00   95
 18  \w     83.00 178.00   1.00    1.00    --  109.13  45.00 -30.00   95
 19  \w     81.00 178.00   1.00    1.00    --  109.13  30.00 120.00   97
 20  \w    -70.00  31.00   1.00    1.00    --  -41.80  57.00  60.00  101
 21  \w   -118.00  -9.00   1.00    1.00    --  -41.80 -77.00  90.00  109
 22  \w     23.00  98.00   1.00    1.00    --   41.80-125.00-120.00   75
 23  \w     77.00 178.00   1.00    1.00    --  109.13  77.00 -90.00  101
 24  \w     77.00 178.00   1.00    1.00    --  109.13  77.00 120.00  101
 25  \w     26.00 109.00   1.00    1.00    --  109.13 -94.00-120.00   83
 26  \w     77.00 178.00   1.00    1.00    --  109.13  77.00   0.00  101
 27  \w     80.00 178.00   1.00    1.00    --  109.13  61.00-120.00   98
 28  \w     80.00 178.00   1.00    1.00    --  109.13  61.00-150.00   98
 29  \w   -118.00  -9.00   1.00    1.00    --  -41.80 -77.00-150.00  109
 30  \w   -116.00 -17.00   1.00    1.00    --  -41.80 -38.00 -90.00   99
 31  \w      9.00 118.00   1.00    1.00    --   41.80  77.00   0.00  109
 32  \w     77.00 178.00   1.00    1.00    --  109.13  77.00  90.00  101
;
_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      0.0360108000
_diffrn_orient_matrix_UB_12      -0.0539923000
_diffrn_orient_matrix_UB_13      -0.0680837000
_diffrn_orient_matrix_UB_21      -0.0460034000
_diffrn_orient_matrix_UB_22      -0.1287783000
_diffrn_orient_matrix_UB_23      0.0236795000
_diffrn_orient_matrix_UB_31      -0.1496744000
_diffrn_orient_matrix_UB_32      0.0265999000
_diffrn_orient_matrix_UB_33      -0.0236534000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0847
_diffrn_reflns_av_unetI/netI     0.0368
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            39897
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.673
_diffrn_reflns_theta_min         4.354
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.836
_exptl_absorpt_correction_T_max  0.979
_exptl_absorpt_correction_T_min  0.952
_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    1.342
_exptl_crystal_description       'rect. Prism'
_exptl_crystal_F_000             896
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.132
_exptl_crystal_size_min          0.092
_refine_diff_density_max         0.193
_refine_diff_density_min         -0.341
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Flack x determined using 1553 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.14(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     283
_refine_ls_number_reflns         4330
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0523
_refine_ls_R_factor_gt           0.0449
_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^)+(0.0682P)^2^+0.4259P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1081
_refine_ls_wR_factor_ref         0.1155
_reflns_Friedel_coverage         0.742
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.979
_reflns_number_gt                3894
_reflns_number_total             4330
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b01241_si_001.cif
_cod_data_source_block           mdh025
_cod_depositor_comments
'Adding full bibliography for 4032851--4032855.cif.'
_cod_database_code               4032855
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C25 H25 F3 N2 O'
_chemical_oxdiff_usercomment     JD598
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1), C3(H3), C4(H4)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C12(H12A,H12B), C19(H19A,H19B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C14(H14), C15(H15), C16(H16),
 C17(H17), C18(H18), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25)
;
_shelx_res_checksum              41665
_shelx_hkl_checksum              74581
_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 1.380
_oxdiff_exptl_absorpt_empirical_full_min 0.751