Asymmetric Barton–Zard Reaction To Access 3-Pyrrole-Containing Axially Chiral Skeletons
He, Xiao-Long; Zhao, Hui-Ru; Song, Xue; Jiang, Bo; Du, Wei; Chen, Ying-Chun; ACS Catalysis 9 (2019) 4374–; doi:10.1021/acscatal.9b00767

data_4514689
_publ_section_title
;
 Asymmetric Barton--Zard Reaction To Access 3-Pyrrole-Containing Axially
 Chiral Skeletons
;
_journal_issue                   5
_journal_name_full               'ACS Catalysis'
_journal_page_first              4374
_journal_paper_doi               10.1021/acscatal.9b00767
_journal_volume                  9
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H20 F3 N O5 S'
_chemical_formula_sum            'C21 H20 F3 N O5 S'
_chemical_formula_weight         455.44
_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     direct
_audit_creation_date             2018-03-09
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90.165(2)
_cell_angle_beta                 95.249(2)
_cell_angle_gamma                115.510(3)
_cell_formula_units_Z            2
_cell_length_a                   9.0328(3)
_cell_length_b                   9.5060(3)
_cell_length_c                   13.9771(3)
_cell_measurement_reflns_used    10200
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      72.5870
_cell_measurement_theta_min      5.1550
_cell_volume                     1077.42(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      140.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.981
_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      3.00  33.00   1.00    1.00    --   36.00  88.00  -4.39   30
  2  \w   -105.00 -17.00   1.00    1.00    --  -36.04 -38.00  60.00   88
  3  \w    -55.00  33.00   1.00    1.00    --  -36.04  38.00-150.00   88
  4  \w    -55.00  33.00   1.00    1.00    --  -36.04  38.00-120.00   88
  5  \w   -105.00 -17.00   1.00    1.00    --  -36.04 -38.00-150.00   88
  6  \w     23.00  89.00   1.00    1.00    --   36.04-125.00  60.00   66
  7  \w     -1.00  25.00   1.00    1.00    --   36.04  95.00 121.83   26
  8  \w      1.00  75.00   1.00    1.00    --   36.04 -99.00   0.00   74
  9  \w    -31.00  53.00   1.00    1.00    --   36.04 -57.00 -90.00   84
 10  \w     23.00  89.00   1.00    1.00    --   36.04-125.00 150.00   66
 11  \w     23.00  89.00   1.00    1.00    --   36.04-125.00 -60.00   66
 12  \w    -33.00 105.00   1.00    1.00    --   36.04   0.00   0.00  138
 13  \w      8.00  34.00   1.00    1.00    --   40.00  87.00 -58.64   26
 14  \w      6.00  32.00   1.00    1.00    --   40.00  90.00-149.00   26
 15  \w     14.00  40.00   1.00    1.00    --   44.00  83.00-124.76   26
 16  \w     15.00  46.00   1.00    1.00    --   44.00  81.00  64.24   31
 17  \w     19.00  46.00   1.00    1.00    --   48.00  81.00 138.19   27
 18  \w     20.00  46.00   1.00    1.00    --   48.00  80.00 -84.72   26
 19  \w     19.00  46.00   1.00    1.00    --   48.00  81.00  96.84   27
 20  \w     26.00 119.00   1.00    1.00    --   52.00  76.00 -51.55   93
 21  \w     25.00 120.00   1.00    1.00    --   52.00  77.00 179.80   95
 22  \w     26.00 119.00   1.00    1.00    --   52.00  76.00 140.43   93
 23  \w     26.00 119.00   1.00    1.00    --   52.00  75.00  18.23   93
 24  \w     29.00 124.00   1.00    1.00    --   56.00  77.00 -79.99   95
 25  \w     30.00 123.00   1.00    1.00    --   56.00  75.00-118.53   93
 26  \w     32.00 123.00   1.00    1.00    --   56.00  72.00  76.45   91
 27  \w     34.00 127.00   1.00    1.00    --   60.00  75.00 -21.23   93
 28  \w     63.00 148.00   1.00    1.00    --   80.00  47.00-138.27   85
 29  \w     82.00 176.00   1.00    1.00    --  108.71  77.00  60.00   94
 30  \w     82.00 176.00   1.00    1.00    --  108.71  77.00   0.00   94
 31  \w     42.00 127.00   1.00    1.00    --  108.71 -61.00   0.00   85
 32  \w     91.00 176.00   1.00    1.00    --  108.71  61.00  90.00   85
 33  \w     42.00 127.00   1.00    1.00    --  108.71 -61.00 120.00   85
 34  \w     91.00 176.00   1.00    1.00    --  108.71  61.00 -60.00   85
 35  \w     82.00 176.00   1.00    1.00    --  108.71  77.00 -30.00   94
 36  \w     82.00 176.00   1.00    1.00    --  108.71  77.00-180.00   94
 37  \w     82.00 176.00   1.00    1.00    --  108.71  77.00 -60.00   94
 38  \w     82.00 176.00   1.00    1.00    --  108.71  77.00-150.00   94
 39  \w     41.00 135.00   1.00    1.00    --  108.71 -77.00-120.00   94
 40  \w     39.00 115.00   1.00    1.00    --  108.71-111.00-120.00   76
 41  \w     82.00 176.00   1.00    1.00    --  108.71  77.00 150.00   94
 42  \w     82.00 176.00   1.00    1.00    --  108.71  77.00  90.00   94
 43  \w     91.00 176.00   1.00    1.00    --  108.71  61.00 -30.00   85
 44  \w     39.00 115.00   1.00    1.00    --  108.71-111.00 150.00   76
 45  \w     82.00 176.00   1.00    1.00    --  108.71  77.00 120.00   94
 46  \w     82.00 108.00   1.00    1.00    --  108.71  77.00 -90.00   26
 47  \w     92.00 125.00   1.00    1.00    --  108.71  61.00  60.00   33
 48  \w     44.00 108.00   1.00    1.00    --  108.71 -94.00  30.00   64
 49  \w     82.00 109.00   1.00    1.00    --  108.71  77.00  30.00   27
 50  \w     93.00 173.00   1.00    1.00    --  108.71  61.00 150.00   80
 51  \w     82.00 109.00   1.00    1.00    --  108.71  77.00-120.00   27
 52  \w     91.00 173.00   1.00    1.00    --  108.71  61.00  30.00   82
 53  \w     91.00 121.00   1.00    1.00    --  108.71  61.00-120.00   30
 54  \w    131.00 165.00   1.00    1.00    --  108.71  61.00-120.00   34
 55  \w     91.00 173.00   1.00    1.00    --  108.71  61.00 -90.00   82
 56  \w    141.00 167.00   1.00    1.00    --  108.71  61.00   0.00   26
 57  \w     91.00 137.00   1.00    1.00    --  108.71  61.00   0.00   46
 58  \w     91.00 168.00   1.00    1.00    --  108.71  61.00 120.00   77
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0348346000
_diffrn_orient_matrix_UB_12      0.0539432000
_diffrn_orient_matrix_UB_13      0.1071021000
_diffrn_orient_matrix_UB_21      0.1788845000
_diffrn_orient_matrix_UB_22      0.1112558000
_diffrn_orient_matrix_UB_23      -0.0158415000
_diffrn_orient_matrix_UB_31      -0.0536562000
_diffrn_orient_matrix_UB_32      0.1304941000
_diffrn_orient_matrix_UB_33      -0.0235868000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0330
_diffrn_reflns_av_unetI/netI     0.0291
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            21432
_diffrn_reflns_point_group_measured_fraction_full 0.905
_diffrn_reflns_point_group_measured_fraction_max 0.881
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.095
_diffrn_reflns_theta_min         5.161
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.867
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.35813
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.404
_exptl_crystal_description       block
_exptl_crystal_F_000             472
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.55
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.790
_refine_diff_density_min         -0.547
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Flack x determined using 3045 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.026(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     567
_refine_ls_number_reflns         7615
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0659
_refine_ls_R_factor_gt           0.0640
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1080P)^2^+0.8971P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1717
_refine_ls_wR_factor_ref         0.1746
_reflns_Friedel_coverage         0.796
_reflns_Friedel_fraction_full    0.811
_reflns_Friedel_fraction_max     0.781
_reflns_number_gt                7335
_reflns_number_total             7615
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b00767_si_002.cif
_cod_data_source_block           3d
_cod_database_code               4514689
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 99.97
_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 N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C01Q, C01J, C01O
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
C01Q \\sim C01J \\sim C01O: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002
4.a Aromatic/amide H refined with riding coordinates:
 N00A(H00A), N00B(H00B), C00L(H00L), C00S(H00S), C00W(H00W), C00X(H00X),
 C00Z(H00Z), C012(H012), C016(H016), C017(H017), C019(H019), C01B(H01N),
 C01D(H01D), C01F(H01R), C01H(H01S), C01I(H01T)
4.b Idealised Me refined as rotating group:
 C013(H01A,H01B,H01C), C01E(H01O,H01P,H01Q), C01G(H01E,H01F,H01G), C01K(H01H,
 H01I,H01J), C01M(H01K,H01L,H01M), C01N(H01U,H01V,H01W), C01O(H01X,H01Y,H),
 C01Q(H01Z,HA,HB)
;
_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 2.011
_oxdiff_exptl_absorpt_empirical_full_min 0.629