N-Heterocyclic carbene catalyzed desymmetrization of diols: access to enantioenriched oxindoles having a C3-quaternary stereocenter.
Dutta, Sourav; Porey, Arka; Guin, Joyram; Chemical communications (Cambridge, England) 59 (2023) 5771–5774; doi:10.1039/d3cc00489a

data_7131533
_publ_section_title
;
 N-Heterocyclic carbene catalyzed desymmetrization of diols: access to
 enantioenriched oxindoles having a C3-quaternary stereocenter.
;
_journal_issue                   38
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              5771
_journal_page_last               5774
_journal_paper_doi               10.1039/d3cc00489a
_journal_volume                  59
_journal_year                    2023
_chemical_absolute_configuration Rmod
_chemical_formula_moiety         'C18 H15 Br I N O4'
_chemical_formula_sum            'C18 H15 Br I N O4'
_chemical_formula_weight         513.12
_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   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2022-12-27
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-12-27 deposited with the CCDC.	2023-04-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.8468(4)
_cell_length_b                   10.3709(4)
_cell_length_c                   17.4196(8)
_cell_measurement_reflns_used    9953
_cell_measurement_temperature    134.31
_cell_measurement_theta_max      27.51
_cell_measurement_theta_min      2.38
_cell_volume                     1778.89(13)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      134.31
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0615
_diffrn_reflns_av_unetI/netI     0.0447
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            20967
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.526
_diffrn_reflns_theta_min         2.285
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.069
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.2265
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1575 before and 0.0937 after correction.
The Ratio of minimum to maximum transmission is 0.3038.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear whiteish white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.927
_exptl_crystal_description       plate
_exptl_crystal_F_000             1000
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.098
_refine_diff_density_min         -0.653
_refine_diff_density_rms         0.098
_refine_ls_abs_structure_details
;
 Flack x determined using 1637 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.117(6)
_refine_ls_extinction_coef       0.0051(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     229
_refine_ls_number_reflns         4089
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0283
_refine_ls_R_factor_gt           0.0270
_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^)+(0.0236P)^2^+0.9398P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0638
_refine_ls_wR_factor_ref         0.0643
_reflns_Friedel_coverage         0.752
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                3965
_reflns_number_total             4089
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc00489a2.cif
_cod_data_source_block           mo_jgocarka280421_0m_a
_cod_depositor_comments
;
          Adding full bibliography for 7131533.cif.

2025-03-31
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C72 H60 Br4 I4 N4 O16'
_cod_original_formula_weight         2064.48
_cod_original_formula_moiety         '4(C18 H15 Br I N O4)'
_cod_original_formula_units_Z            1
_cod_database_code               7131533
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.686
_shelx_estimated_absorpt_t_min   0.235
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C9(H9A,H9B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C7(H7), C8(H8), C10(H10), C14(H14), C17(H17), C18(H18)
2.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C)
2.d Idealised tetrahedral OH refined as rotating group:
 O3(H3)
;
_shelx_res_checksum              47437
_shelx_hkl_checksum              8550
_olex2_submission_special_instructions 'No special instructions were received'