Synthesis of bioactive fluoropyrrolidines via copper(i)-catalysed asymmetric 1,3-dipolar cycloaddition of azomethine ylides
Xu, Xiao; Bao, Longzhu; Ran, Lu; Yang, Zhenyan; Yan, Dingce; Wang, Chun-Jiang; Teng, Huailong; Chemical Science 13 (2022) 1398–1407; doi:10.1039/D1SC04595D

data_1565590
_publ_section_title
;
 Synthesis of bioactive fluoropyrrolidines via copper(i)-catalysed
 asymmetric 1,3-dipolar cycloaddition of azomethine ylides
;
_journal_issue                   5
_journal_name_full               'Chemical Science'
_journal_page_first              1398
_journal_page_last               1407
_journal_paper_doi               10.1039/D1SC04595D
_journal_volume                  13
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H15 Br Cl F2 N O2'
_chemical_formula_sum            'C18 H15 Br Cl F2 N O2'
_chemical_formula_weight         430.67
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-12-15
_audit_creation_method
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_audit_update_record
;
2021-02-23 deposited with the CCDC.	2021-12-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.3848(7)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.04668(8)
_cell_length_b                   5.51936(5)
_cell_length_c                   14.34857(10)
_cell_measurement_reflns_used    8163
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.4030
_cell_measurement_theta_min      4.0760
_cell_volume                     857.627(12)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.982
_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    141.00 176.00   0.50    0.50    --   94.60  18.00 -53.00   70
  2  \w     21.00  60.00   0.50    0.50    --   94.60 -18.00 137.00   78
  3  \w     71.00 104.00   0.50    0.50    --   94.60 -18.00 137.00   66
  4  \w     88.00 131.00   0.50    0.50    --   94.60  18.00 -53.00   86
  5  \w     28.00  54.00   0.50    0.50    --    0.00  18.00 -53.00   52
  6  \w    -20.00  22.00   0.50    0.50    --    0.00 -16.00  25.47   84
  7  \w    -27.00  27.00   0.50    0.50    --    0.00 -77.00-180.00  108
  8  \w    -17.00  37.00   0.50    0.50    --    0.00  38.00  60.00  108
  9  \w     50.00  76.00   0.50    0.50    --    0.00  38.00  60.00   52
 10  \w    -29.00  28.00   0.50    0.50    --    0.00 -82.00 -90.00  114
 11  \w    -35.00 -10.00   0.50    0.50    --    0.00 -18.00 137.00   50
 12  \w    146.00 172.00   0.50    0.50    --   94.60  61.00 -30.00   52
 13  \w     71.00  96.00   0.50    0.50    --   94.60  61.00 -30.00   50
 14  \w      9.00  35.00   0.50    0.50    --   94.60 -61.00   0.00   52
 15  \w     71.00 106.00   0.50    0.50    --   94.60  60.00  69.66   70
 16  \w     72.00 138.00   0.50    0.50    --   94.60  61.00   0.00  132
 17  \w    143.00 184.00   0.50    0.50    --   94.60  61.00   0.00   82
 18  \w     71.00 102.00   0.50    0.50    --   94.60  61.00  30.00   62
 19  \w      7.00 107.00   0.50    0.50    --   94.60 -77.00 -60.00  200
 20  \w     68.00  93.00   0.50    0.50    --   94.60  69.00  38.05   50
 21  \w     80.00 129.00   0.50    0.50    --   94.60  30.00 120.00   98
 22  \w     69.00  94.00   0.50    0.50    --   94.60  67.00   7.57   50
 23  \w     71.00  98.00   0.50    0.50    --   94.60  61.00  90.00   54
 24  \w     79.00 105.00   0.50    0.50    --   94.60  45.00   0.00   52
 25  \w     72.00  98.00   0.50    0.50    --   94.60  61.00  60.00   52
 26  \w     74.00 118.00   0.50    0.50    --   94.60 -61.00 -90.00   88
 27  \w     79.00 179.00   0.50    0.50    --   94.60  30.00   0.00  200
 28  \w     76.00 110.00   0.50    0.50    --   94.60  45.00  60.00   68
 29  \w     72.00  97.00   0.50    0.50    --   94.60  61.00 120.00   50
 30  \w    131.00 176.00   0.50    0.50    --   94.60  61.00 120.00   90
 31  \w    153.00 179.00   0.50    0.50    --   94.60  61.00  30.00   52
 32  \w     78.00 126.00   0.50    0.50    --   94.60  30.00  90.00   96
 33  \w     76.00 102.00   0.50    0.50    --   94.60  45.00 -30.00   52
 34  \w     21.00 113.00   0.50    0.50    --   94.60 -45.00   0.00  184
 35  \w     50.00  91.00   0.50    0.50    --   94.60 -61.00   0.00   82
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1131900000
_diffrn_orient_matrix_UB_12      0.0491405000
_diffrn_orient_matrix_UB_13      -0.0450081000
_diffrn_orient_matrix_UB_21      -0.0858844000
_diffrn_orient_matrix_UB_22      0.0439012000
_diffrn_orient_matrix_UB_23      -0.0969385000
_diffrn_orient_matrix_UB_31      -0.0066230000
_diffrn_orient_matrix_UB_32      0.2712839000
_diffrn_orient_matrix_UB_33      0.0238819000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0161
_diffrn_reflns_av_unetI/netI     0.0135
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            8948
_diffrn_reflns_point_group_measured_fraction_full 0.956
_diffrn_reflns_point_group_measured_fraction_max 0.930
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.909
_diffrn_reflns_theta_min         3.142
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.001
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47477
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
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    1.668
_exptl_crystal_description       prism
_exptl_crystal_F_000             432
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.198
_refine_diff_density_min         -0.342
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 1332 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.006(7)
_refine_ls_extinction_coef       0.0075(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     232
_refine_ls_number_reflns         3235
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0176
_refine_ls_R_factor_gt           0.0176
_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^)+(0.0306P)^2^+0.2243P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0465
_refine_ls_wR_factor_ref         0.0466
_reflns_Friedel_coverage         0.708
_reflns_Friedel_fraction_full    0.904
_reflns_Friedel_fraction_max     0.865
_reflns_number_gt                3233
_reflns_number_total             3235
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc04595d4.cif
_cod_data_source_block           20201214_1
_cod_depositor_comments          'Adding full bibliography for 1565590.cif.'
_cod_original_cell_volume        857.627(11)
_cod_database_code               1565590
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.690
_shelx_estimated_absorpt_t_min   0.240
_reflns_odcompleteness_completeness 99.94
_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
2.a Ternary CH refined with riding coordinates:
 C00A(H00A), C00H(H00H), C00N(H00N)
2.b Aromatic/amide H refined with riding coordinates:
 C00B(H00B), C00C(H00C), C00D(H00D), C00F(H00F), C00J(H00J), C00K(H00K),
 C00L(H00L), C00P(H00P)
2.c Idealised Me refined as rotating group:
 C00M(H00E,H00G,H00I)
;
_shelx_res_checksum              47221
_shelx_hkl_checksum              58824
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.080
_oxdiff_exptl_absorpt_empirical_full_min 0.645