Kinetic Resolution of 2-Substituted 1,2-Dihydroquinolines via Asymmetric Cu-Catalyzed Borylation Reaction
Kong, Duanyang; Han, Suna; Wang, Rui; Li, Meina; Zi, Guofu; Hou, Gouhua; Chem. Sci.  (2017) –; doi:10.1039/C7SC01556A

data_1545761
_publ_section_title
;
 Kinetic Resolution of 2-Substituted 1,2-Dihydroquinolines via Asymmetric
 Cu-Catalyzed Borylation Reaction
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC01556A
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C27 H30 B N O4'
_chemical_formula_sum            'C27 H30 B N O4'
_chemical_formula_weight         443.33
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_block_doi                 10.5517/ccdc.csd.cc1nsd72
_audit_creation_date             2017-03-24
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2017-04-07 deposited with the CCDC.
2017-04-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.52078(10)
_cell_length_b                   15.6118(2)
_cell_length_c                   17.5200(2)
_cell_measurement_reflns_used    7541
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.1500
_cell_measurement_theta_min      5.0400
_cell_volume                     2330.59(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3127
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.985
_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    -62.00  32.00   1.00    1.00    --  -41.49  57.00 -90.00   94
  2  \w    -22.00   5.00   1.00    1.00    --   41.49 -48.00-127.00   27
  3  \w     42.00  68.00   1.00    1.00    --   41.49 -48.00-127.00   26
  4  \w    121.00 175.00   1.00    1.00    --  107.52  30.00-180.00   54
  5  \w     86.00 173.00   1.00    1.00    --  107.52  61.00-150.00   87
  6  \w     75.00 159.00   1.00    1.00    --  107.52  77.00 -60.00   84
  7  \w     97.00 154.00   1.00    1.00    --  107.52 125.00  60.00   57
  8  \w     42.00 137.00   1.00    1.00    --  107.52 -61.00  60.00   95
  9  \w     27.00  98.00   1.00    1.00    --  107.52 -94.00  60.00   71
 10  \w     24.00  51.00   1.00    1.00    --   41.49-125.00  90.00   27
 11  \w    -60.00  13.00   1.00    1.00    --  -41.49  37.00-180.00   73
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1128988000
_diffrn_orient_matrix_UB_12      -0.0689633000
_diffrn_orient_matrix_UB_13      0.0307967000
_diffrn_orient_matrix_UB_21      -0.1375990000
_diffrn_orient_matrix_UB_22      0.0439150000
_diffrn_orient_matrix_UB_23      -0.0412120000
_diffrn_orient_matrix_UB_31      0.0310731000
_diffrn_orient_matrix_UB_32      -0.0554650000
_diffrn_orient_matrix_UB_33      -0.0712547000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0186
_diffrn_reflns_av_unetI/netI     0.0236
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            9699
_diffrn_reflns_point_group_measured_fraction_full 0.962
_diffrn_reflns_point_group_measured_fraction_max 0.936
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.363
_diffrn_reflns_theta_min         3.792
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.665
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67732
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.263
_exptl_crystal_description       block
_exptl_crystal_F_000             944
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.329
_refine_diff_density_min         -0.290
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 1678 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.03(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     303
_refine_ls_number_reflns         4390
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0324
_refine_ls_R_factor_gt           0.0316
_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^)+(0.0406P)^2^+0.5597P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0795
_refine_ls_wR_factor_ref         0.0802
_reflns_Friedel_coverage         0.670
_reflns_Friedel_fraction_full    0.911
_reflns_Friedel_fraction_max     0.872
_reflns_number_gt                4277
_reflns_number_total             4390
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc01556a2.cif
_cod_data_source_block           2a
_cod_original_cell_volume        2330.58(5)
_cod_database_code               1545761
_chemical_oxdiff_formula         C1H1N1B1O1
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.13
_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
2.a Ternary CH refined with riding coordinates:
 C7(H7), C17(H17)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B)
2.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13), C19(H19), C20(H20), C21(H21),
 C23(H23), C24(H24), C25(H25), C26(H26)
2.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C16(H16A,
 H16B,H16C)
;
_shelx_res_checksum              4599
_shelx_hkl_checksum              55265
_shelx_shelxl_version_number     2014/7
_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 1.546
_oxdiff_exptl_absorpt_empirical_full_min 0.673