Organo-Cation Catalyzed Asymmetric Homo/Heterodialkylation of Bisoxindoles: Construction of Vicinal All-Carbon Quaternary Stereocenters and Total Synthesis of (-)-Chimonanthidine.
Chen, Si-Kai; Ma, Wen-Qiang; Yan, Zhi-Bo; Zhang, Fu-Min; Wang, Shao-Hua; Tu, Yong-Qiang; Zhang, Xiao-Ming; Tian, Jin-Miao; Journal of the American Chemical Society 140 (2018) 10099–10103; doi:10.1021/jacs.8b05386

data_4132657
_publ_section_title
;
 Organo-Cation Catalyzed Asymmetric Homo/Heterodialkylation of
 Bisoxindoles: Construction of Vicinal All-Carbon Quaternary Stereocenters
 and Total Synthesis of (-)-Chimonanthidine.
;
_journal_issue                   32
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10099
_journal_page_last               10103
_journal_paper_doi               10.1021/jacs.8b05386
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'Br, C H Cl3, C25 H27 N4 O3'
_chemical_formula_sum            'C26 H28 Br Cl3 N4 O3'
_chemical_formula_weight         630.78
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-06-09
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                110.886(12)
_cell_angle_beta                 93.340(10)
_cell_angle_gamma                100.809(12)
_cell_formula_units_Z            1
_cell_length_a                   8.9983(11)
_cell_length_b                   9.3045(15)
_cell_length_c                   9.3473(10)
_cell_measurement_reflns_used    1060
_cell_measurement_temperature    245(6)
_cell_measurement_theta_max      21.7170
_cell_measurement_theta_min      4.1100
_cell_volume                     711.50(18)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_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_temperature      245(6)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega  -81.00    0.00   1.5000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.5055  -57.0000   30.0000 54

  2 omega  -19.00   24.50   1.5000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.5055  -98.0000  -72.0000 29

  3 omega  -47.00   46.00   1.5000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867  -57.0000  120.0000 62

  4 omega  -48.00    0.00   1.5000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867  -57.0000    0.0000 32

  5 omega   -1.00   92.00   1.5000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867   57.0000  -90.0000 62

  6 omega   69.00   96.00   1.5000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867  178.0000   90.0000 18
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0724903000
_diffrn_orient_matrix_UB_12      -0.0220806000
_diffrn_orient_matrix_UB_13      0.0215985000
_diffrn_orient_matrix_UB_21      0.0244406000
_diffrn_orient_matrix_UB_22      -0.0610860000
_diffrn_orient_matrix_UB_23      0.0168818000
_diffrn_orient_matrix_UB_31      0.0266427000
_diffrn_orient_matrix_UB_32      0.0528010000
_diffrn_orient_matrix_UB_33      0.0772666000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0312
_diffrn_reflns_av_unetI/netI     0.0762
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            4509
_diffrn_reflns_theta_full        26.02
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.39
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.761
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93713
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.472
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description
;
;
_exptl_crystal_F_000             322
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.278
_refine_diff_density_min         -0.267
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.002(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     336
_refine_ls_number_reflns         3860
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0709
_refine_ls_R_factor_gt           0.0479
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0229P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0880
_refine_ls_wR_factor_ref         0.1008
_reflns_number_gt                2913
_reflns_number_total             3860
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja8b05386_si_001.cif
_cod_data_source_block           chensk_0605
_cod_original_cell_volume        711.49(17)
_cod_database_code               4132657
_chemical_oxdiff_formula         'C H O Br N'
_reflns_odcompleteness_completeness 99.76
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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.a Ternary CH refined with riding coordinates:
 C26(H26)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C11(H11A,H11B)
2.c Aromatic/amide H refined with riding coordinates:
 N4(H4), C7(H7), C10(H10), C13(H13), C14(H14), C15(H15), C16(H16), C17(H17),
 C20(H20), C21(H21), C22(H22)
2.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C)
;
_olex2_date_sample_data_collection 2017-06-05
_olex2_submission_special_instructions 'No special instructions were received'