Asymmetric Synthesis of Multifunctionalized 2,3-Benzodiazepines by a One-pot N-Heterocyclic Carbene/Chiral Palladium Sequential Catalysis.
Ding, Ya-Li; Zhao, Yun-Long; Niu, Shuang-Shuo; Wu, Pei; Cheng, Ying; The Journal of organic chemistry  (2019) –; doi:10.1021/acs.joc.9b02693

data_4037704
_publ_section_title
;
 Asymmetric Synthesis of Multifunctionalized 2,3-Benzodiazepines by a
 One-pot N-Heterocyclic Carbene/Chiral Palladium Sequential Catalysis.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.9b02693
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C15 H14 Cl N3 O6'
_chemical_formula_sum            'C15 H14 Cl N3 O6'
_chemical_formula_weight         367.74
_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     dual
_audit_creation_date             2019-06-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   8.35980(10)
_cell_length_b                   11.94590(10)
_cell_length_c                   32.5899(4)
_cell_measurement_reflns_used    13545
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.9850
_cell_measurement_theta_min      3.9550
_cell_volume                     3254.60(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.972
_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   -114.00 -31.00   0.10    0.10    --  -47.70 -65.00  92.00  830
  2  \w   -172.00-142.00   0.10    0.10    -- -102.00 -56.00-102.00  300
  3  \w   -106.00 -29.00   0.10    0.10    -- -102.00  65.00-131.00  770
  4  \w     45.00  95.00   0.10    0.10    --  104.75-121.00  24.00  500
  5  \w   -116.00 -88.00   0.10    0.10    --  -47.70-125.00  30.00  280
  6  \w   -108.00 -82.00   0.10    0.10    --  -47.70-125.00-150.00  260
  7  \w     -5.00  31.00   0.10    0.10    --   47.70 -19.00 -90.00  360
  8  \w   -175.00-143.00   0.10    0.10    -- -102.00 -30.00-150.00  320
  9  \w   -144.00 -96.00   0.10    0.10    -- -102.00 -30.00 120.00  480
 10  \w   -166.00 -88.00   0.10    0.10    -- -102.00 -15.00 -30.00  780
 11  \w   -126.00 -89.00   0.10    0.10    -- -102.00 -30.00-150.00  370
 12  \w   -175.00-150.00   0.10    0.10    -- -102.00 -30.00 120.00  250
 13  \w     34.00  59.00   0.10    0.10    --  104.75 -94.00  60.00  250
 14  \w    101.00 176.00   0.10    0.10    --  104.75  45.00-180.00  750
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0739892000
_diffrn_orient_matrix_UB_12      -0.0926543000
_diffrn_orient_matrix_UB_13      0.0268433000
_diffrn_orient_matrix_UB_21      -0.1673624000
_diffrn_orient_matrix_UB_22      0.0300203000
_diffrn_orient_matrix_UB_23      -0.0164413000
_diffrn_orient_matrix_UB_31      0.0216898000
_diffrn_orient_matrix_UB_32      -0.0845207000
_diffrn_orient_matrix_UB_33      -0.0352726000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0365
_diffrn_reflns_av_unetI/netI     0.0370
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            15719
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.943
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.343
_diffrn_reflns_theta_min         2.712
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.443
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84993
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.35a (Rigaku Oxford Diffraction, 2018)
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    1.501
_exptl_crystal_description       block
_exptl_crystal_F_000             1520
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.299
_refine_diff_density_min         -0.301
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Flack x determined using 2394 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.005(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.099
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     455
_refine_ls_number_reflns         6356
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.099
_refine_ls_R_factor_all          0.0367
_refine_ls_R_factor_gt           0.0315
_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^)+(0.0340P)^2^+1.5656P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0770
_refine_ls_wR_factor_ref         0.0834
_reflns_Friedel_coverage         0.710
_reflns_Friedel_fraction_full    0.957
_reflns_Friedel_fraction_max     0.905
_reflns_number_gt                6070
_reflns_number_total             6356
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02693_si_002.cif
_cod_data_source_block           20190605d
_cod_database_code               4037704
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         c1h1n1o1Cl1
_shelx_estimated_absorpt_t_max   0.792
_shelx_estimated_absorpt_t_min   0.641
_diffrn_oxdiff_digest_frames
;
015b991b5d2fc8fdb5c6048012c73b013106500fe10
;
_diffrn_oxdiff_digest_hkl
;
01f51b41985444fba5ae4c242160387901605f
;
_reflns_odcompleteness_completeness 99.37
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C13(H13), C28(H28)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C5(H5), C6(H6), C7(H7), C14(H14), C17(H17), C20(H20), C21(H21),
 C22(H22), C29(H29)
2.c X=CH2 refined with riding coordinates:
 C15(H15A,H15B), C30(H30A,H30B)
2.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C25(H25A,H25B,H25C), C27(H27A,H27B,
 H27C)
;
_shelx_res_checksum              70452
_shelx_hkl_checksum              76284
_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 1.280
_oxdiff_exptl_absorpt_empirical_full_min 0.864