Organocatalyzed enantioselective Michael addition/cyclization cascade reaction of 3-isothiocyanato oxindoles with arylidene malonates.
Chowdhury, Raghunath; Kumar, Mukesh; Ghosh, Sunil K.; Organic & biomolecular chemistry 14 (2016) 11250–11260; doi:10.1039/c6ob02104b

data_7155359
_publ_section_title
;
 Organocatalyzed enantioselective Michael addition/cyclization cascade
 reaction of 3-isothiocyanato oxindoles with arylidene malonates.
;
_journal_issue                   47
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              11250
_journal_page_last               11260
_journal_paper_doi               10.1039/c6ob02104b
_journal_volume                  14
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H19 Br N2 O5 S, 2(C3 H8 O)'
_chemical_formula_sum            'C28 H35 Br N2 O7 S'
_chemical_formula_weight         623.55
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-07-22
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2016-08-26 deposited with the CCDC.
2016-11-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.05634(18)
_cell_length_b                   11.2038(2)
_cell_length_c                   30.5045(5)
_cell_measurement_reflns_used    15076
_cell_measurement_temperature    293
_cell_measurement_theta_max      72.8300
_cell_measurement_theta_min      3.9380
_cell_volume                     3095.15(10)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (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_temperature      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 4.1600
_diffrn_detector_type            Titan
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.989
_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    -26.00  60.00   1.00    1.00    --   43.29 -57.00-120.00   86
  2  \w     69.00 133.00   1.00    2.00    --  102.90 -77.00 -90.00   64
  3  \w     92.00 155.00   1.00    2.00    --  102.90  30.00  90.00   63
  4  \w     94.00 145.00   1.00    2.00    --  102.90  61.00 150.00   51
  5  \w     90.00 156.00   1.00    2.00    --  102.90  45.00 120.00   66
  6  \w     80.00 158.00   1.00    2.00    --  102.90  88.00  12.00   78
  7  \w    116.00 154.00   1.00    2.00    --  102.90  61.00 -60.00   38
  8  \w     95.00 147.00   1.00    2.00    --  102.90  77.00-120.00   52
  9  \w     39.00 124.00   1.00    2.00    --  102.90 -30.00-120.00   85
 10  \w     33.00 100.00   1.00    2.00    --  102.90 -95.00 -90.00   67
 11  \w     32.00  63.00   1.00    2.00    --  102.90 -77.00 -90.00   31
 12  \w     23.00 106.00   1.00    2.00    --  102.90 -95.00-180.00   83
 13  \w     13.00 118.00   1.00    1.00    --   43.29  77.00   0.00  105
 14  \w     18.00  83.00   1.00    1.00    --   43.29  57.00 120.00   65
 15  \w     31.00 122.00   1.00    2.00    --  102.90-126.00 120.00   91
 16  \w    -88.00 -35.00   1.00    1.00    --  -43.29 -57.00 -90.00   53
 17  \w   -113.00 -86.00   1.00    1.00    --  -43.29 -99.00   0.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Titan'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1090605000
_diffrn_orient_matrix_UB_12      -0.0641494000
_diffrn_orient_matrix_UB_13      -0.0307707000
_diffrn_orient_matrix_UB_21      0.1092721000
_diffrn_orient_matrix_UB_22      0.0148283000
_diffrn_orient_matrix_UB_23      -0.0383327000
_diffrn_orient_matrix_UB_31      0.0713623000
_diffrn_orient_matrix_UB_32      -0.1207111000
_diffrn_orient_matrix_UB_33      0.0116328000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0561
_diffrn_reflns_av_unetI/netI     0.0343
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            21644
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.330
_diffrn_reflns_theta_min         2.897
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.815
_exptl_absorpt_correction_T_max  0.506
_exptl_absorpt_correction_T_min  0.136
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
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    1.338
_exptl_crystal_description       plate
_exptl_crystal_F_000             1296
_exptl_crystal_size_max          0.75
_exptl_crystal_size_mid          0.635
_exptl_crystal_size_min          0.338
_refine_diff_density_max         0.764
_refine_diff_density_min         -0.528
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Flack x determined using 1960 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.008(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     361
_refine_ls_number_reflns         6083
_refine_ls_number_restraints     26
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0622
_refine_ls_R_factor_gt           0.0542
_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^)+(0.0960P)^2^+1.0238P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1486
_refine_ls_wR_factor_ref         0.1603
_reflns_Friedel_coverage         0.745
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.967
_reflns_number_gt                5322
_reflns_number_total             6083
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6ob02104b3.cif
_cod_data_source_block           spiroxaindole1_1
_cod_depositor_comments          'Adding full bibliography for 7155359.cif.'
_cod_original_cell_volume        3095.14(10)
_cod_database_code               7155359
_chemical_oxdiff_formula         'C28 N2 O7 H35 Br S'
_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, All O(H) groups
2. Restrained distances
 C24-C23 = C25-C24
 1.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C23 \\sim C24 \\sim C25: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C28 \\sim C27 \\sim C26: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
4.a Ternary CH refined with riding coordinates:
 C7(H7), C24(H24), C27(H27)
4.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C2(H2), C3(H3), C4(H4), C6(H6), C19(H19), C20(H20), C21(H21), C22(H22)
4.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C16(H16A,H16B,H16C), C23(H23A,H23B,
 H23C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C)
4.d Idealised tetrahedral OH refined as rotating group:
 O6(H6A), O7(H7A)
;
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-07-21
_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 3.358
_oxdiff_exptl_absorpt_empirical_full_min 0.302