Enantioselective synthesis of 3-hydroxy- and 3-amino-3-alkynyl-2-oxindoles by the dimethylzinc-mediated addition of terminal alkynes to isatins and isatin-derived ketimines.
Prieto, Elena; Martín, Jorge D; Nieto, Javier; Andrés, Celia; Organic & biomolecular chemistry 21 (2023) 6940–6948; doi:10.1039/d3ob01023f

data_7159516
_publ_section_title
;
 Enantioselective synthesis of 3-hydroxy- and
 3-amino-3-alkynyl-2-oxindoles by the dimethylzinc-mediated addition of
 terminal alkynes to isatins and isatin-derived ketimines.
;
_journal_issue                   34
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              6940
_journal_page_last               6948
_journal_paper_doi               10.1039/d3ob01023f
_journal_volume                  21
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C30 H20 Cl4 N2 O2'
_chemical_formula_sum            'C30 H20 Cl4 N2 O2'
_chemical_formula_weight         582.28
_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             2021-04-19
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-07-19 deposited with the CCDC.	2023-08-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.147(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.1758(3)
_cell_length_b                   5.34020(10)
_cell_length_c                   21.8778(6)
_cell_measurement_reflns_used    3548
_cell_measurement_temperature    298.15
_cell_measurement_theta_max      74.6930
_cell_measurement_theta_min      3.8310
_cell_volume                     1395.68(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      298.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4757
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.979
_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    -89.00   1.00   1.00   13.82    --  -41.06 122.00-123.00   90
  2  \w    -70.00 -44.00   1.00   13.82    --  -41.06 178.00-120.00   26
  3  \w   -111.00  -8.00   1.00   13.82    --  -41.06 -77.00 150.00  103
  4  \w    -68.00 -39.00   1.00   13.82    --  -41.06 178.00 150.00   29
  5  \w   -100.00 -17.00   1.00   13.82    --  -41.06 -57.00  30.00   83
  6  \w     75.00 134.00   1.00   55.29    --  110.01 -30.00   0.00   59
  7  \w     35.00  60.00   1.00   55.29    --  110.01 -30.00   0.00   25
  8  \w     38.00 134.00   1.00   55.29    --  110.01 -45.00 -90.00   96
  9  \w     65.00 108.00   1.00   55.29    --  110.01-125.00  60.00   43
 10  \w     47.00 116.00   1.00   55.29    --  110.01-125.00 -90.00   69
 11  \w     48.00 115.00   1.00   55.29    --  110.01 -30.00  90.00   67
 12  \w    119.00 165.00   1.00   55.29    --  110.01  30.00-120.00   46
 13  \w     34.00  59.00   1.00   55.29    --  110.01 -94.00 -90.00   25
 14  \w     76.00 110.00   1.00   55.29    --  110.01 -94.00 -90.00   34
 15  \w    102.00 127.00   1.00   55.29    --  110.01 125.00 150.00   25
 16  \w     88.00 114.00   1.00   55.29    --  110.01-122.00 154.00   26
 17  \w    107.00 175.00   1.00   55.29    --  110.01  45.00  30.00   68
 18  \w     79.00 145.00   1.00   55.29    --  110.01 151.00  37.00   66
 19  \w     36.00 141.00   1.00   55.29    --  110.01 -77.00  60.00  105
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0352677000
_diffrn_orient_matrix_UB_12      0.2769990000
_diffrn_orient_matrix_UB_13      0.0004528000
_diffrn_orient_matrix_UB_21      0.1226958000
_diffrn_orient_matrix_UB_22      0.0755010000
_diffrn_orient_matrix_UB_23      0.0245245000
_diffrn_orient_matrix_UB_31      0.0178146000
_diffrn_orient_matrix_UB_32      0.0292937000
_diffrn_orient_matrix_UB_33      -0.0674591000
_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  0.0237
_diffrn_reflns_av_unetI/netI     0.0355
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            9628
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.059
_diffrn_reflns_theta_min         3.700
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.102
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.539
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
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    1.386
_exptl_crystal_description       needle
_exptl_crystal_F_000             596
_exptl_crystal_size_max          0.411
_exptl_crystal_size_mid          0.052
_exptl_crystal_size_min          0.045
_refine_diff_density_max         0.327
_refine_diff_density_min         -0.496
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1827 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.003(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     344
_refine_ls_number_reflns         5556
_refine_ls_number_restraints     49
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0532
_refine_ls_R_factor_gt           0.0457
_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^)+(0.0452P)^2^+0.4413P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1139
_refine_ls_wR_factor_ref         0.1205
_reflns_Friedel_coverage         0.765
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.938
_reflns_number_gt                4885
_reflns_number_total             5556
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob01023f2.cif
_cod_data_source_block           el1345b
_cod_depositor_comments
'Adding full bibliography for 7159515--7159516.cif.'
_cod_database_code               7159516
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C30 H20 Cl4 N2 O2'
_chemical_oxdiff_usercomment     colorless
_shelx_estimated_absorpt_t_max   0.837
_shelx_estimated_absorpt_t_min   0.283
_reflns_odcompleteness_completeness 99.93
_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 C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C10, C11, C12, C13, C14, C15
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 1.7A
4.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B)
4.b Aromatic/amide H refined with riding coordinates:
 N2(H2), C4(H4), C5(H5), C6(H6), C7(H7), C12(H12), C13(H13), C14(H14),
 C24(H24), C26(H26), C27(H27), C28(H28), C31(H31), C33(H33), C35(H35)
4.c Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C)
;
_shelx_res_checksum              15844
_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 1.332
_oxdiff_exptl_absorpt_empirical_full_min 0.696