Organocatalytic Asymmetric Mannich Addition of 3-Fluorooxindoles to Dibenzo[<i>b</i>,<i>f</i>][1,4]oxazepines: Highly Enantioselective Construction of Tetrasubstituted C-F Stereocenters.
Li, Bing-Yu; Lin, Ye; Du, Da-Ming; The Journal of organic chemistry 84 (2019) 11752–11762; doi:10.1021/acs.joc.9b01507

data_4034460
_publ_section_title
;
 Organocatalytic Asymmetric Mannich Addition of 3-Fluorooxindoles to
 Dibenzo[<i>b</i>,<i>f</i>][1,4]oxazepines: Highly Enantioselective
 Construction of Tetrasubstituted C-F Stereocenters.
;
_journal_issue                   18
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              11752
_journal_page_last               11762
_journal_paper_doi               10.1021/acs.joc.9b01507
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H16 Br F N2 O2'
_chemical_formula_sum            'C22 H16 Br F N2 O2'
_chemical_formula_weight         439.28
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2019-06-05
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
????
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.5425(17)
_cell_length_b                   11.979(2)
_cell_length_c                   17.812(4)
_cell_measurement_reflns_used    6529
_cell_measurement_temperature    163(2)
_cell_measurement_theta_max      27.4855
_cell_measurement_theta_min      2.0488
_cell_volume                     1822.7(6)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      163.15
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'multiwire proportional'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0494
_diffrn_reflns_av_unetI/netI     0.0488
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            12210
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.483
_diffrn_reflns_theta_min         2.644
_exptl_absorpt_coefficient_mu    2.286
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7724
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2008)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.601
_exptl_crystal_description       block
_exptl_crystal_F_000             888
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.316
_refine_diff_density_min         -0.656
_refine_diff_density_rms         0.068
_refine_ls_abs_structure_details
;
 Flack x determined using 1463 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.033(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     254
_refine_ls_number_reflns         4130
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0457
_refine_ls_R_factor_gt           0.0430
_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^)+(0.0346P)^2^+1.4934P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0948
_refine_ls_wR_factor_ref         0.0967
_reflns_Friedel_coverage         0.749
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                3936
_reflns_number_total             4130
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b01507_si_002.cif
_cod_data_source_block           bwn19253
_cod_database_code               4034460
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.645
_shelx_estimated_absorpt_t_min   0.567
_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
2.a Riding coordinates:
 N5(H5)
2.b Ternary CH refined with riding coordinates:
 C14(H14)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C8(H8), C15(H15), C19(H19), C20(H20), C24(H24), C25(H25), C26(H26),
 C27(H27), C28(H28), C29(H29)
2.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C)
;
_olex2_submission_special_instructions 'No special instructions were received'