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_1565567
_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         'C25 H22 F4 N2 O'
_chemical_formula_sum            'C25 H22 F4 N2 O'
_chemical_formula_weight         442.44
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-03-26
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.3110(2)
_cell_length_b                   12.3464(2)
_cell_length_c                   34.9989(7)
_cell_measurement_reflns_used    16755
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.9130
_cell_measurement_theta_min      2.4940
_cell_volume                     4455.49(14)
_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 0.981
_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    -23.00  26.00   0.50    4.00    --  -46.62  19.00 -60.00   98
  2  \w    -67.00 -41.00   0.50   15.00    -- -100.00  61.00-180.00   52
  3  \w    -67.00 -30.00   0.50   15.00    -- -100.00  61.00-150.00   74
  4  \w    -94.00 -29.00   0.50   15.00    -- -100.00  91.00  18.00  130
  5  \w     34.00 102.00   0.50    4.00    --   46.62  44.00 169.00  136
  6  \w   -104.00 -78.00   0.50    4.00    --  -46.62-125.00 -60.00   52
  7  \w   -112.00 -74.00   0.50    4.00    --  -46.62-125.00 150.00   76
  8  \w     59.00  88.00   0.50   15.00    --  105.44 -94.00 166.00   58
  9  \w     95.00 178.00   0.50   15.00    --  105.44  44.00 169.00  166
 10  \w     39.00  69.00   0.50   15.00    --  105.44 -61.00-120.00   60
 11  \w     71.00 102.00   0.50   15.00    --  105.44 -94.00-150.00   62
 12  \w     38.00  64.00   0.50   15.00    --  105.44 -61.00 -30.00   52
 13  \w     37.00  73.00   0.50   15.00    --  105.44 -61.00 -60.00   72
 14  \w     91.00 136.00   0.50   20.00    --  105.44  94.00 -82.00   90
 15  \w    -39.00 -13.00   0.50    6.00    --  -46.37  38.00-120.00   52
 16  \w     -2.00  24.00   0.50    6.00    --  -46.37  38.00-120.00   52
 17  \w     -9.00  28.00   0.50    6.00    --   46.37 -19.00  30.00   74
 18  \w   -132.00 -94.00   0.50   20.00    -- -100.00 -45.00-150.00   76
 19  \w    -55.00 -29.00   0.50   20.00    -- -100.00 125.00-150.00   52
 20  \w    -97.00 -68.00   0.50   20.00    -- -100.00 125.00-150.00   58
 21  \w     33.00  59.00   0.50   20.00    --  105.44 -61.00 -90.00   52
 22  \w     78.00 110.00   0.50   20.00    --  105.44-125.00 120.00   64
 23  \w     39.00  68.00   0.50   20.00    --  105.44 -61.00-150.00   58
 24  \w     34.00  61.00   0.50   20.00    --  105.44-125.00 120.00   54
 25  \w     92.00 130.00   0.50   20.00    --  105.44  45.00-180.00   76
 26  \w    138.00 165.00   0.50   20.00    --  105.44  45.00-180.00   54
 27  \w     42.00  68.00   0.50   20.00    --  105.44 -61.00-180.00   52
 28  \w     44.00  70.00   0.50   20.00    --  105.44 -61.00   0.00   52
 29  \w    138.00 164.00   0.50   20.00    --  105.44  94.00 -82.00   52
 30  \w     30.00 118.00   0.50    6.00    --   46.37  57.00  60.00  176
 31  \w     30.00 118.00   0.50    6.00    --   46.37  57.00-120.00  176
 32  \w     18.00  95.00   0.50    6.00    --   46.37-125.00 120.00  154
 33  \w     23.00 118.00   0.50    6.00    --   46.37  77.00 150.00  190
 34  \w     23.00  48.00   0.50    6.00    --   46.37  77.00   0.00   50
 35  \w     30.00 118.00   0.50    6.00    --   46.37  57.00 -30.00  176
 36  \w    -49.00 -24.00   0.50    6.00    --  -46.37  91.00  18.00   50
 37  \w    -49.00 -24.00   0.50    6.00    --  -46.37  91.00  18.00   50
 38  \w      2.00  27.00   0.50    6.00    --   46.37 -91.00 -94.00   50
 39  \w    -49.00 -24.00   0.50    6.00    --  -46.37  91.00  18.00   50
 40  \w    -49.00 -24.00   0.50    6.00    --  -46.37  91.00  18.00   50
 41  \w     35.00  61.00   0.50   20.00    --  107.00 -94.00 166.00   52
 42  \w     43.00  69.00   0.50   20.00    --  107.00-125.00 150.00   52
 43  \w     84.00 110.00   0.50   20.00    --  107.00-125.00 150.00   52
 44  \w     83.00 108.00   0.50   20.00    --  107.00  77.00-150.00   50
 45  \w    137.00 175.00   0.50   20.00    --  107.00  77.00-150.00   76
 46  \w     45.00  76.00   0.50   20.00    --  107.00 -77.00-120.00   62
 47  \w     85.00 111.00   0.50   20.00    --  107.00  77.00-180.00   52
 48  \w    125.00 174.00   0.50   20.00    --  107.00  77.00-180.00   98
 49  \w     37.00  63.00   0.50   20.00    --  107.00 -77.00-180.00   52
 50  \w     34.00  64.00   0.50   20.00    --  107.00 -94.00   0.00   60
 51  \w     42.00  68.00   0.50   20.00    --  107.00 -77.00 -90.00   52
 52  \w     78.00 104.00   0.50   20.00    --  107.00 -94.00 166.00   52
;
_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      0.1076116000
_diffrn_orient_matrix_UB_12      0.0049250000
_diffrn_orient_matrix_UB_13      -0.0304619000
_diffrn_orient_matrix_UB_21      -0.0844292000
_diffrn_orient_matrix_UB_22      -0.0681313000
_diffrn_orient_matrix_UB_23      -0.0272719000
_diffrn_orient_matrix_UB_31      -0.0600572000
_diffrn_orient_matrix_UB_32      0.1043956000
_diffrn_orient_matrix_UB_33      -0.0163454000
_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  0.1344
_diffrn_reflns_av_unetI/netI     0.0712
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            55083
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.255
_diffrn_reflns_theta_min         2.525
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.881
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73121
_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    1.319
_exptl_crystal_description       plate
_exptl_crystal_F_000             1840
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.290
_refine_diff_density_min         -0.278
_refine_diff_density_rms         0.059
_refine_ls_abs_structure_details
;
 Flack x determined using 2600 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.11(8)
_refine_ls_extinction_coef       0.00057(12)
_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   1.051
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     590
_refine_ls_number_reflns         9142
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0718
_refine_ls_R_factor_gt           0.0517
_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^)+(0.0612P)^2^+1.2463P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1200
_refine_ls_wR_factor_ref         0.1343
_reflns_Friedel_coverage         0.764
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.951
_reflns_number_gt                7302
_reflns_number_total             9142
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc05174a2.cif
_cod_data_source_block           20210325-zwr-1
_cod_depositor_comments
;Adding full bibliography for 1565565--1565567.cif.

 Adding full bibliography for 1565565--1565567.cif.
;
_cod_database_code               1565567
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.957
_shelx_estimated_absorpt_t_min   0.879
_reflns_odcompleteness_completeness 99.98
_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.a Aromatic/amide H refined with riding coordinates:
 N41(H41), N63(H63), N23(H23), C27(H27), C36(H36), C8(H8), C2(H2), C5(H5),
 C58(H58), C7(H7), C38(H38), C33(H33), C60(H60), C24(H24), C39(H39), C55(H55),
 C30(H30), C61(H61), C29(H29)
2.b Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C47(H47A,H47B,H47C), C54(H54A,H54B,H54C), C15(H15A,H15B,
 H15C), C48(H48A,H48B,H48C), C16(H16A,H16B,H16C), C14(H14A,H14B,H14C), C46(H46A,
 H46B,H46C)
;
_shelx_res_checksum              83516
_shelx_hkl_checksum              77895
_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 3.925
_oxdiff_exptl_absorpt_empirical_full_min 0.310