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_7159515
_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         'C18 H13 N O3'
_chemical_formula_sum            'C18 H13 N O3'
_chemical_formula_weight         291.29
_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             2018-02-13
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2020-10-26 deposited with the CCDC.	2023-08-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.957(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.3533(2)
_cell_length_b                   5.06800(10)
_cell_length_c                   13.1835(2)
_cell_measurement_reflns_used    5132
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      74.9790
_cell_measurement_theta_min      3.9350
_cell_volume                     742.10(2)
_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      296.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4757
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_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   -115.00 -17.00   1.00    1.43    --  -40.93 -37.00  60.00   98
  2  \w   -117.00  -8.00   1.00    1.43    --  -40.93 -77.00 120.00  109
  3  \w    -65.00  34.00   1.00    1.43    --  -40.93  37.00 150.00   99
  4  \w   -115.00 -17.00   1.00    1.43    --  -40.93 -37.00 150.00   98
  5  \w   -113.00 -13.00   1.00    1.43    --  -40.93 -57.00 150.00  100
  6  \w      1.00  82.00   1.00    1.43    --   40.93 -99.00  30.00   81
  7  \w     29.00 109.00   1.00    5.70    --  111.26 -94.00-180.00   80
  8  \w     82.00 178.00   1.00    5.70    --  111.26  61.00 120.00   96
  9  \w     38.00 137.00   1.00    5.70    --  111.26 -45.00 -60.00   99
 10  \w     85.00 178.00   1.00    5.70    --  111.26  45.00  90.00   93
 11  \w     79.00 178.00   1.00    5.70    --  111.26  77.00-150.00   99
 12  \w     79.00 178.00   1.00    5.70    --  111.26  77.00 120.00   99
 13  \w     82.00 178.00   1.00    5.70    --  111.26  61.00-180.00   96
 14  \w     79.00 178.00   1.00    5.70    --  111.26  77.00 150.00   99
 15  \w     82.00 178.00   1.00    5.70    --  111.26  61.00-120.00   96
 16  \w     79.00 178.00   1.00    5.70    --  111.26  77.00  90.00   99
 17  \w     79.00 178.00   1.00    5.70    --  111.26  77.00-180.00   99
 18  \w     82.00 178.00   1.00    5.70    --  111.26  61.00  90.00   96
 19  \w     85.00 178.00   1.00    5.70    --  111.26  45.00-120.00   93
 20  \w     94.00 178.00   1.00    5.70    --  111.26 125.00  60.00   84
 21  \w     85.00 178.00   1.00    5.70    --  111.26  45.00 150.00   93
 22  \w     82.00 178.00   1.00    5.70    --  111.26  61.00 150.00   96
 23  \w     29.00 109.00   1.00    5.70    --  111.26 -94.00-120.00   80
 24  \w     85.00 178.00   1.00    5.70    --  111.26  45.00-180.00   93
 25  \w     85.00 178.00   1.00    5.70    --  111.26  45.00-150.00   93
 26  \w     85.00 178.00   1.00    5.70    --  111.26  45.00 120.00   93
 27  \w     83.00 178.00   1.00    5.70    --  111.26  30.00-120.00   95
 28  \w     81.00 178.00   1.00    5.70    --  111.26  65.00-152.83   97
 29  \w     82.00 178.00   1.00    5.70    --  111.26  60.00 155.75   96
 30  \w   -128.00 -34.00   1.00    1.43    --  -40.93 178.00 120.00   94
 31  \w   -113.00 -13.00   1.00    1.43    --  -40.93 -57.00 -30.00  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1344772000
_diffrn_orient_matrix_UB_12      0.0678050000
_diffrn_orient_matrix_UB_13      0.0121007000
_diffrn_orient_matrix_UB_21      0.0168054000
_diffrn_orient_matrix_UB_22      -0.0233192000
_diffrn_orient_matrix_UB_23      0.1185900000
_diffrn_orient_matrix_UB_31      0.0295365000
_diffrn_orient_matrix_UB_32      -0.2955072000
_diffrn_orient_matrix_UB_33      -0.0066767000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0272
_diffrn_reflns_av_unetI/netI     0.0190
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            13704
_diffrn_reflns_point_group_measured_fraction_full 0.950
_diffrn_reflns_point_group_measured_fraction_max 0.930
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.597
_diffrn_reflns_theta_min         3.427
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.731
_exptl_absorpt_correction_T_max  0.959
_exptl_absorpt_correction_T_min  0.892
_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    1.304
_exptl_crystal_description       prism
_exptl_crystal_F_000             304
_exptl_crystal_size_max          0.275
_exptl_crystal_size_mid          0.112
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.108
_refine_diff_density_min         -0.106
_refine_diff_density_rms         0.024
_refine_ls_abs_structure_details
;
 Flack x determined using 1001 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(13)
_refine_ls_extinction_coef       0.0053(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     202
_refine_ls_number_reflns         2887
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0369
_refine_ls_R_factor_gt           0.0329
_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^)+(0.0445P)^2^+0.0507P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0854
_refine_ls_wR_factor_ref         0.0893
_reflns_Friedel_coverage         0.677
_reflns_Friedel_fraction_full    0.886
_reflns_Friedel_fraction_max     0.850
_reflns_number_gt                2637
_reflns_number_total             2887
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob01023f2.cif
_cod_data_source_block           3ca
_cod_depositor_comments
'Adding full bibliography for 7159515--7159516.cif.'
_cod_database_code               7159515
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C18 H13 N1 O3'
_shelx_estimated_absorpt_t_max   0.957
_shelx_estimated_absorpt_t_min   0.824
_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
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C3(H3A), C4(H4), C5(H5), C6(H6), C14(H14), C15(H15), C16(H16), C17(H17),
 C18(H18)
2.b Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C)
2.c Idealised tetrahedral OH refined as rotating group:
 O3(H3)
;
_shelx_res_checksum              98001
_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 1.436
_oxdiff_exptl_absorpt_empirical_full_min 0.588