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_1565565
_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         'C22 H17 F3 N2 O'
_chemical_formula_sum            'C22 H17 F3 N2 O'
_chemical_formula_weight         382.37
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-03-24
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-08-05 deposited with the CCDC.	2021-11-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.3790(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.40350(10)
_cell_length_b                   10.62490(10)
_cell_length_c                   9.51730(10)
_cell_measurement_reflns_used    16928
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.7630
_cell_measurement_theta_min      4.6680
_cell_volume                     946.698(17)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_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      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_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     23.00  72.00   0.50    0.08    --   46.37  77.00 -90.00   98
  2  \w     23.00 118.00   0.50    0.08    --   46.37  77.00   0.00  190
  3  \w     30.00 118.00   0.50    0.08    --   46.37  57.00 120.00  176
  4  \w     79.00 178.00   0.50    0.50    --  107.00 125.00  60.00  198
  5  \w     79.00 178.00   0.50    0.50    --  107.00 125.00  30.00  198
  6  \w     89.00 178.00   0.50    0.50    --  107.00 105.00 -33.00  178
  7  \w     93.00 178.00   0.50    0.50    --  107.00  45.00  60.00  170
  8  \w     93.00 178.00   0.50    0.50    --  107.00  45.00  30.00  170
  9  \w     93.00 178.00   0.50    0.50    --  107.00  45.00-180.00  170
 10  \w    -27.00  45.00   0.50    0.08    --   46.37 -38.00 -30.00  144
 11  \w     34.00 107.00   0.50    0.50    --  107.00 -77.00  90.00  146
 12  \w     34.00  73.00   0.50    0.50    --  107.00 -61.00  30.00   78
 13  \w     34.00  73.00   0.50    0.50    --  107.00 -61.00   0.00   78
 14  \w     34.00 106.00   0.50    0.50    --  107.00 -94.00 -90.00  144
 15  \w     34.00 112.00   0.50    0.50    --  107.00-125.00-150.00  156
 16  \w     34.00 112.00   0.50    0.50    --  107.00-125.00-180.00  156
 17  \w     18.00  95.00   0.50    0.08    --   46.37-125.00-120.00  154
 18  \w     34.00 112.00   0.50    0.50    --  107.00-125.00 -30.00  156
 19  \w     34.00 112.00   0.50    0.50    --  107.00-125.00   0.00  156
 20  \w     34.00 112.00   0.50    0.50    --  107.00-125.00  30.00  156
 21  \w     34.00 112.00   0.50    0.50    --  107.00-125.00  60.00  156
 22  \w     34.00 112.00   0.50    0.50    --  107.00-125.00 120.00  156
 23  \w     34.00 112.00   0.50    0.50    --  107.00-125.00 150.00  156
 24  \w     34.00 107.00   0.50    0.50    --  107.00-105.00-133.00  146
 25  \w     34.00 106.00   0.50    0.50    --  107.00 -94.00-120.00  144
 26  \w      2.00  84.00   0.50    0.08    --   46.37-105.00-133.00  164
 27  \w   -173.00 -84.00   0.50    0.50    -- -100.00 -55.00 139.42  178
 28  \w   -118.00 -23.00   0.50    0.08    --  -46.37 -77.00-180.00  190
 29  \w   -173.00 -76.00   0.50    0.50    -- -100.00 -77.00-180.00  194
 30  \w   -107.00 -27.00   0.50    0.50    -- -100.00 105.00 -33.00  160
 31  \w    -84.00   2.00   0.50    0.08    --  -46.37 105.00 -33.00  172
 32  \w   -173.00 -79.00   0.50    0.50    -- -100.00 -69.00 -30.26  188
 33  \w   -173.00 -77.00   0.50    0.50    -- -100.00 -75.00-111.07  192
 34  \w   -173.00 -84.00   0.50    0.50    -- -100.00-105.00-133.00  178
 35  \w    -69.00 -27.00   0.50    0.50    -- -100.00  61.00-180.00   84
 36  \w    -69.00 -27.00   0.50    0.50    -- -100.00  61.00 -90.00   84
 37  \w   -103.00 -27.00   0.50    0.50    -- -100.00  77.00  90.00  152
 38  \w    -69.00 -27.00   0.50    0.50    -- -100.00  61.00 150.00   84
 39  \w    -41.00  27.00   0.50    0.08    --  -46.37  38.00 150.00  136
;
_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      0.0291489000
_diffrn_orient_matrix_UB_12      -0.0164824000
_diffrn_orient_matrix_UB_13      -0.1555687000
_diffrn_orient_matrix_UB_21      -0.0397695000
_diffrn_orient_matrix_UB_22      0.1388824000
_diffrn_orient_matrix_UB_23      -0.0287236000
_diffrn_orient_matrix_UB_31      0.1569777000
_diffrn_orient_matrix_UB_32      0.0382329000
_diffrn_orient_matrix_UB_33      0.0376165000
_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  0.0419
_diffrn_reflns_av_unetI/netI     0.0295
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            19789
_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         76.763
_diffrn_reflns_theta_min         4.667
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.873
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86976
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
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    1.341
_exptl_crystal_description       block
_exptl_crystal_F_000             396
_refine_diff_density_max         0.214
_refine_diff_density_min         -0.188
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 1744 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(4)
_refine_ls_extinction_coef       0.0039(7)
_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   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     256
_refine_ls_number_reflns         3896
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0307
_refine_ls_R_factor_gt           0.0302
_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^)+(0.0389P)^2^+0.1569P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0767
_refine_ls_wR_factor_ref         0.0771
_reflns_Friedel_coverage         0.875
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.971
_reflns_number_gt                3823
_reflns_number_total             3896
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc05174a2.cif
_cod_data_source_block           zhuwr_210323
_cod_depositor_comments
;Adding full bibliography for 1565565--1565567.cif.

 Adding full bibliography for 1565565--1565567.cif.
;
_cod_database_code               1565565
_shelx_shelxl_version_number     2018/3
_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:
 N13(H13), C11(H11), C5(H5), C17(H17), C8(H8), C7(H7), C14(H14), C12(H12),
 C20(H20), C18(H18), C19(H19)
2.b Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C)
;
_shelx_res_checksum              49573
_shelx_hkl_checksum              63766
_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 1.828
_oxdiff_exptl_absorpt_empirical_full_min 0.540