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_1545762
_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         'C25 H32 B N O6'
_chemical_formula_sum            'C25 H32 B N O6'
_chemical_formula_weight         453.32
_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.cc1nsd61
_audit_creation_date             2017-03-28
_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                   11.0936(3)
_cell_length_b                   14.6662(2)
_cell_length_c                   14.7500(2)
_cell_measurement_reflns_used    3556
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.1360
_cell_measurement_theta_min      4.9710
_cell_volume                     2399.84(8)
_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 0.999
_diffrn_measured_fraction_theta_max 0.983
_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   -106.00  10.00   1.00    2.00    --  -41.49   0.00-150.00  116
  2  \w     27.00 109.00   1.00   10.00    --  107.52 -94.00-150.00   82
  3  \w     82.00 170.00   1.00   10.00    --  107.52  30.00  90.00   88
  4  \w     78.00 176.00   1.00   10.00    --  107.52  77.00 150.00   98
  5  \w     26.00  52.00   1.00    2.00    --   41.74-125.00 -60.00   26
  6  \w     31.00  72.00   1.00    2.00    --   41.74-125.00 150.00   41
  7  \w    140.00 178.00   1.00   10.00    --  107.52  77.00  60.00   38
  8  \w    135.00 162.00   1.00   10.00    --  107.52 125.00-150.00   27
  9  \w    122.00 148.00   1.00   10.00    --  107.52  77.00 -60.00   26
;
_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      -0.0771509000
_diffrn_orient_matrix_UB_12      0.0330613000
_diffrn_orient_matrix_UB_13      -0.0804254000
_diffrn_orient_matrix_UB_21      -0.0952958000
_diffrn_orient_matrix_UB_22      -0.0731037000
_diffrn_orient_matrix_UB_23      0.0222598000
_diffrn_orient_matrix_UB_31      -0.0651283000
_diffrn_orient_matrix_UB_32      0.0677539000
_diffrn_orient_matrix_UB_33      0.0628998000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0313
_diffrn_reflns_av_unetI/netI     0.0462
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            7673
_diffrn_reflns_point_group_measured_fraction_full 0.933
_diffrn_reflns_point_group_measured_fraction_max 0.899
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.281
_diffrn_reflns_theta_min         4.251
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.718
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69659
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.255
_exptl_crystal_description       block
_exptl_crystal_F_000             968
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.171
_refine_diff_density_min         -0.199
_refine_diff_density_rms         0.041
_refine_ls_abs_structure_details
;
 Flack x determined using 1462 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     305
_refine_ls_number_reflns         4326
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0394
_refine_ls_R_factor_gt           0.0353
_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^)+(0.0388P)^2^+0.2235P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0832
_refine_ls_wR_factor_ref         0.0858
_reflns_Friedel_coverage         0.618
_reflns_Friedel_fraction_full    0.848
_reflns_Friedel_fraction_max     0.791
_reflns_number_gt                4025
_reflns_number_total             4326
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc01556a2.cif
_cod_data_source_block           2p
_cod_original_cell_volume        2399.83(8)
_cod_database_code               1545762
_chemical_oxdiff_formula         c1h1n1o1B1
_reflns_odcompleteness_completeness 99.88
_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:
 C1(H1), C2(H2)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C7(H7), C8(H8), C12(H12), C13(H13), C15(H15), C16(H16)
2.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C22(H22A,H22B,
 H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              54878
_shelx_hkl_checksum              61089
_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 1.386
_oxdiff_exptl_absorpt_empirical_full_min 0.598