Organocatalytic enantioselective S<sub>N</sub>1-type dehydrative nucleophilic substitution: access to bis(indolyl)methanes bearing quaternary carbon stereocenters.
Zhu, Wen-Run; Su, Qiong; Deng, Xiao-Yi; Liu, Jia-Sheng; Zhong, Tao; Meng, Shan-Shui; Yi, Ji-Tao; Weng, Jiang; Lu, Gui; Chemical science 13 (2021) 170–177; doi:10.1039/d1sc05174a

data_1565566
_publ_section_title
;
 Organocatalytic enantioselective S<sub>N</sub>1-type dehydrative
 nucleophilic substitution: access to bis(indolyl)methanes bearing
 quaternary carbon stereocenters.
;
_journal_issue                   1
_journal_name_full               'Chemical science'
_journal_page_first              170
_journal_page_last               177
_journal_paper_doi               10.1039/d1sc05174a
_journal_volume                  13
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C27 H18 Br F3 N2'
_chemical_formula_sum            'C27 H18 Br F3 N2'
_chemical_formula_weight         507.34
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-10-07
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2021-08-05 deposited with the CCDC.	2021-11-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.1505(2)
_cell_length_b                   19.0261(9)
_cell_length_c                   11.5778(4)
_cell_measurement_reflns_used    7727
_cell_measurement_temperature    300.28(15)
_cell_measurement_theta_max      74.4370
_cell_measurement_theta_min      3.8130
_cell_volume                     2235.96(14)
_computing_cell_refinement       'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      300.28(15)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_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   -127.00 -27.00   0.50    3.00    -- -100.00  85.00-140.00  200
  2  \w   -173.00 -82.00   0.50    3.00    -- -100.00-103.00  10.00  182
  3  \w   -174.00 -85.00   0.50    3.00    -- -100.00 -43.00-131.00  178
  4  \w   -119.00 -71.00   0.50    0.30    --  -46.62-125.00   0.00   96
  5  \w   -119.00 -71.00   0.50    0.30    --  -46.62-125.00  60.00   96
  6  \w    -27.00  61.00   0.50    0.30    --   46.62 -38.00 120.00  176
  7  \w     32.00 123.00   0.50    3.00    --  107.00 -30.00 120.00  182
  8  \w     83.00 178.00   0.50    3.00    --  107.00  77.00 150.00  190
  9  \w     93.00 178.00   0.50    3.00    --  107.00  45.00 -30.00  170
 10  \w     93.00 178.00   0.50    3.00    --  107.00  45.00 -60.00  170
 11  \w     34.00 109.00   0.50    3.00    --  107.00 -94.00-180.00  150
 12  \w     34.00 109.00   0.50    3.00    --  107.00 -94.00-150.00  150
 13  \w     34.00 109.00   0.50    3.00    --  107.00 -94.00-120.00  150
 14  \w     34.00 109.00   0.50    3.00    --  107.00 -94.00 -60.00  150
 15  \w     34.00 109.00   0.50    3.00    --  107.00 -94.00 150.00  150
 16  \w     23.00  75.00   0.50    0.30    --   46.62  77.00 120.00  104
 17  \w     23.00 120.00   0.50    0.30    --   46.62  77.00-120.00  194
 18  \w    -26.00  61.00   0.50    0.30    --   46.62 -43.00-131.00  174
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0470217000
_diffrn_orient_matrix_UB_12      -0.0671917000
_diffrn_orient_matrix_UB_13      0.0616923000
_diffrn_orient_matrix_UB_21      -0.0676919000
_diffrn_orient_matrix_UB_22      0.0247268000
_diffrn_orient_matrix_UB_23      0.1118239000
_diffrn_orient_matrix_UB_31      -0.1274328000
_diffrn_orient_matrix_UB_32      -0.0378954000
_diffrn_orient_matrix_UB_33      -0.0371645000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0950
_diffrn_reflns_av_unetI/netI     0.0497
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            22787
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.813
_diffrn_reflns_theta_min         4.470
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.876
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86865
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.54a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.507
_exptl_crystal_description       block
_exptl_crystal_F_000             1024
_exptl_crystal_size_max          0.075
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.569
_refine_diff_density_min         -0.653
_refine_diff_density_rms         0.078
_refine_ls_abs_structure_details
;
 Flack x determined using 1282 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.03(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.111
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     299
_refine_ls_number_reflns         4631
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.111
_refine_ls_R_factor_all          0.0832
_refine_ls_R_factor_gt           0.0748
_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^)+(0.0923P)^2^+2.9016P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2167
_refine_ls_wR_factor_ref         0.2233
_reflns_Friedel_coverage         0.742
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.968
_reflns_number_gt                3875
_reflns_number_total             4631
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc05174a2.cif
_cod_data_source_block           zhuwr_201007
_cod_depositor_comments
;Adding full bibliography for 1565565--1565567.cif.

 Adding full bibliography for 1565565--1565567.cif.
;
_cod_database_code               1565566
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHNOBr
_shelx_estimated_absorpt_t_max   0.870
_shelx_estimated_absorpt_t_min   0.813
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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.a Aromatic/amide H refined with riding coordinates:
 N008(H008), C00D(H00D), C00K(H00K), C00L(H00L), C00M(H00M), C00N(H00N),
 C00O(H00O), C00Q(H00Q), C00R(H00R), C00S(H00S), C00T(H00T), C00U(H00U),
 C00V(H00V), C00W(H00W), C00X(H00X)
2.b Idealised Me refined as rotating group:
 C00F(H00A,H00B,H00C)
;
_shelx_res_checksum              35485
_shelx_hkl_checksum              10896
_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 1.278
_oxdiff_exptl_absorpt_empirical_full_min 0.793