An organocatalytic asymmetric Friedel-Crafts reaction of 2-substituted indoles with aldehydes: enantioselective synthesis of α-hydroxyl ketones by low loading of chiral phosphoric acid.
Deng, Xiong-Fei; Wang, Ying-Wei; Zhang, Shi-Qi; Li, Ling; Li, Guang-Xun; Zhao, Gang; Tang, Zhuo; Chemical communications (Cambridge, England) 56 (2020) 2499–2502; doi:10.1039/c9cc09637j

data_7125863
_publ_section_title
;
 An organocatalytic asymmetric Friedel-Crafts reaction of 2-substituted
 indoles with aldehydes: enantioselective synthesis of \a-hydroxyl ketones
 by low loading of chiral phosphoric acid.
;
_journal_issue                   16
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              2499
_journal_page_last               2502
_journal_paper_doi               10.1039/c9cc09637j
_journal_volume                  56
_journal_year                    2020
_chemical_formula_moiety         'C20 H21 N O2'
_chemical_formula_sum            'C20 H21 N O2'
_chemical_formula_weight         307.38
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2019-09-23
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-12-01 deposited with the CCDC.	2020-01-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.846(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.3043(11)
_cell_length_b                   9.7587(7)
_cell_length_c                   12.3878(7)
_cell_measurement_reflns_used    8365
_cell_measurement_temperature    295.9(2)
_cell_measurement_theta_max      71.8450
_cell_measurement_theta_min      5.5050
_cell_volume                     1663.5(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      295.9(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0243
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 1.000
_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    -90.00  -3.00   1.00    1.00    --  -35.97 126.00-150.00   87
  2  \w   -105.00 -17.00   1.00    1.00    --  -35.97 -38.00  60.00   88
  3  \w    -65.00  35.00   1.00    1.00    --  -35.97  19.00-120.00  100
  4  \w      1.00  75.00   1.00    1.00    --   35.97 -99.00 150.00   74
  5  \w     27.00  92.00   1.00    1.00    --   35.97-129.00-141.00   65
  6  \w      1.00  75.00   1.00    1.00    --   35.97 -99.00  30.00   74
  7  \w     17.00 105.00   1.00    1.00    --   35.97  38.00   0.00   88
  8  \w     33.00 100.00   1.00    1.00    --   35.97-143.00  47.00   67
  9  \w     39.00 110.00   1.00    1.77    --  107.97 -95.00  60.00   71
 10  \w     87.00 178.00   1.00    1.77    --  107.97  30.00-180.00   91
 11  \w     38.00 129.00   1.00    1.77    --  107.97 -30.00   0.00   91
 12  \w     87.00 178.00   1.00    1.77    --  107.97  30.00 -90.00   91
 13  \w    101.00 178.00   1.00    1.77    --  107.97 112.00 150.00   77
 14  \w     39.00 110.00   1.00    1.77    --  107.97 -95.00-120.00   71
 15  \w     39.00 110.00   1.00    1.77    --  107.97 -95.00 150.00   71
 16  \w     91.00 176.00   1.00    1.77    --  107.97  45.00 -30.00   85
 17  \w     40.00 125.00   1.00    1.77    --  107.97 -45.00 120.00   85
 18  \w     40.00 125.00   1.00    1.77    --  107.97 -45.00   0.00   85
 19  \w     40.00 125.00   1.00    1.77    --  107.97 -45.00-150.00   85
 20  \w     40.00 131.00   1.00    1.77    --  107.97-143.00  47.00   91
 21  \w     39.00 110.00   1.00    1.77    --  107.97 -95.00 -90.00   71
 22  \w    -55.00  33.00   1.00    1.00    --  -35.97  38.00   0.00   88
 23  \w   -103.00 -19.00   1.00    1.00    --  -35.97 -57.00-180.00   84
 24  \w   -104.00  -9.00   1.00    1.00    --  -35.97 -77.00  30.00   95
 25  \w   -103.00 -19.00   1.00    1.00    --  -35.97 -57.00-120.00   84
 26  \w    -35.00  65.00   1.00    1.00    --   35.97 -19.00  30.00  100
 27  \w      9.00 104.00   1.00    1.00    --   35.97  77.00-180.00   95
 28  \w     70.00 178.00   1.00    1.77    --  107.97  15.00  90.00  108
 29  \w     81.00 176.00   1.00    1.77    --  107.97  77.00 -30.00   95
 30  \w     81.00 176.00   1.00    1.77    --  107.97  77.00  60.00   95
 31  \w     91.00 176.00   1.00    1.77    --  107.97  45.00 -60.00   85
 32  \w     91.00 176.00   1.00    1.77    --  107.97  45.00-150.00   85
 33  \w     91.00 176.00   1.00    1.77    --  107.97  45.00 120.00   85
 34  \w     81.00 176.00   1.00    1.77    --  107.97  77.00-150.00   95
 35  \w     81.00 176.00   1.00    1.77    --  107.97  77.00 120.00   95
 36  \w     90.00 175.00   1.00    1.77    --  107.97  61.00  90.00   85
 37  \w     90.00 175.00   1.00    1.77    --  107.97  61.00 -90.00   85
 38  \w     91.00 176.00   1.00    1.77    --  107.97  45.00-180.00   85
 39  \w     90.00 175.00   1.00    1.77    --  107.97  61.00   0.00   85
 40  \w   -103.00 -19.00   1.00    1.00    --  -35.97 -57.00  60.00   84
 41  \w   -104.00  -9.00   1.00    1.00    --  -35.97 -77.00 -30.00   95
 42  \w      9.00 104.00   1.00    1.00    --   35.97  77.00 120.00   95
 43  \w     19.00 103.00   1.00    1.00    --   35.97  57.00  60.00   84
 44  \w      9.00 104.00   1.00    1.00    --   35.97  77.00 -60.00   95
 45  \w      9.00 104.00   1.00    1.00    --   35.97  77.00-150.00   95
 46  \w     81.00 176.00   1.00    1.77    --  107.97  77.00  30.00   95
 47  \w     81.00 165.00   1.00    1.77    --  107.97  77.00-120.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0238506000
_diffrn_orient_matrix_UB_12      0.0215368000
_diffrn_orient_matrix_UB_13      0.1279286000
_diffrn_orient_matrix_UB_21      0.1091799000
_diffrn_orient_matrix_UB_22      -0.0125881000
_diffrn_orient_matrix_UB_23      0.0090307000
_diffrn_orient_matrix_UB_31      0.0054464000
_diffrn_orient_matrix_UB_32      0.1558291000
_diffrn_orient_matrix_UB_33      -0.0169913000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1211
_diffrn_reflns_av_unetI/netI     0.0521
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            13947
_diffrn_reflns_point_group_measured_fraction_full 0.864
_diffrn_reflns_point_group_measured_fraction_max 0.872
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.072
_diffrn_reflns_theta_min         3.709
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.623
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.24713
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
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    1.227
_exptl_crystal_description       plate
_exptl_crystal_F_000             656
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: n-Hexane/dichloromethane'
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.45
_exptl_crystal_size_min          0.28
_refine_diff_density_max         0.539
_refine_diff_density_min         -0.417
_refine_diff_density_rms         0.074
_refine_ls_abs_structure_details
;
 Flack x determined using 880 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.1(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.372
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     212
_refine_ls_number_reflns         2594
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.372
_refine_ls_R_factor_all          0.0960
_refine_ls_R_factor_gt           0.0933
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2933
_refine_ls_wR_factor_ref         0.2996
_reflns_Friedel_coverage         0.640
_reflns_Friedel_fraction_full    0.720
_reflns_Friedel_fraction_max     0.726
_reflns_number_gt                2423
_reflns_number_total             2594
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc09637j2.cif
_cod_data_source_block           2019-9-20
_cod_depositor_comments          'Adding full bibliography for 7125863.cif.'
_cod_database_code               7125863
_shelxl_version_number           2014-1
_chemical_oxdiff_formula         'C1 H1 O1 N1'
_shelx_estimated_absorpt_t_max   0.845
_shelx_estimated_absorpt_t_min   0.754
_reflns_odcompleteness_completeness 100.00
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C13(H13)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1A), C20(H20), C4(H4), C3(H3), C16(H16), C19(H19), C1(H1B), C2(H2),
 C18(H18), C17(H17)
2.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C9(H9A,H9B,H9C)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_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 4.744
_oxdiff_exptl_absorpt_empirical_full_min 0.321