A copper-catalyzed three-component reaction of dithioacetals with diazo ketones and ketimines
Sha, Hong-Kai; Qian, Yu; Yang, Xiangji; Dong, Kuiyong; Xu, Xinfang; Hu, Wenhao; Organic & Biomolecular Chemistry  (2022) –; doi:10.1039/D2OB01679F

data_7158920
_publ_section_title
;
 A copper-catalyzed three-component reaction of dithioacetals with diazo
 ketones and ketimines
;
_journal_name_full               'Organic &amp; Biomolecular Chemistry'
_journal_paper_doi               10.1039/D2OB01679F
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C39 H35 Cl N2 O5 S2'
_chemical_formula_sum            'C39 H35 Cl N2 O5 S2'
_chemical_formula_weight         711.26
_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             2021-02-09
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2021-08-25 deposited with the CCDC.	2022-10-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.7902(2)
_cell_length_b                   15.7345(4)
_cell_length_c                   21.2170(6)
_cell_measurement_reflns_used    8569
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.3550
_cell_measurement_theta_min      3.4760
_cell_volume                     3602.19(15)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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     92.00 178.00   0.50    1.00    --  107.00  30.00  30.00  172
  2  \w     90.00 178.00   0.50    1.00    --  107.00  61.00 120.00  176
  3  \w     67.00 118.00   0.50    0.50    --   46.37 143.00 122.00  102
  4  \w     92.00 178.00   0.50    1.00    --  107.00  20.00-103.00  172
  5  \w     31.00 122.00   0.50    0.50    --   46.37  20.00-103.00  182
  6  \w     34.00 106.00   0.50    1.00    --  107.00 -94.00-120.00  144
  7  \w     34.00 107.00   0.50    1.00    --  107.00-105.00 -43.00  146
  8  \w     34.00 112.00   0.50    1.00    --  107.00-125.00   0.00  156
  9  \w     34.00  73.00   0.50    1.00    --  107.00 -61.00  60.00   78
 10  \w     34.00  73.00   0.50    1.00    --  107.00 -61.00   0.00   78
 11  \w     34.00 107.00   0.50    1.00    --  107.00 -77.00 -30.00  146
 12  \w     34.00 107.00   0.50    1.00    --  107.00 -77.00 -60.00  146
 13  \w     34.00  73.00   0.50    1.00    --  107.00 -61.00 -30.00   78
 14  \w     34.00  73.00   0.50    1.00    --  107.00 -61.00-120.00   78
 15  \w     34.00  72.00   0.50    1.00    --  107.00 -61.00-150.00   76
 16  \w     34.00  73.00   0.50    1.00    --  107.00 -61.00-180.00   78
 17  \w    -27.00  45.00   0.50    0.50    --   46.37 -38.00 -60.00  144
 18  \w    -29.00  29.00   0.50    0.50    --   46.37 -20.00  89.00  116
 19  \w    -24.00  29.00   0.50    0.50    --  -46.37  19.00 150.00  106
 20  \w    -69.00 -27.00   0.50    1.00    -- -100.00  61.00 150.00   84
 21  \w    -69.00 -27.00   0.50    1.00    -- -100.00  61.00-180.00   84
 22  \w    -24.00  29.00   0.50    0.50    --  -46.37  19.00-120.00  106
 23  \w   -107.00 -27.00   0.50    1.00    -- -100.00 105.00  56.00  160
 24  \w   -125.00 -27.00   0.50    1.00    -- -100.00 143.00 122.00  196
;
_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      -0.0378465000
_diffrn_orient_matrix_UB_12      -0.0091202000
_diffrn_orient_matrix_UB_13      0.0696743000
_diffrn_orient_matrix_UB_21      0.0045881000
_diffrn_orient_matrix_UB_22      0.0973446000
_diffrn_orient_matrix_UB_23      0.0076253000
_diffrn_orient_matrix_UB_31      -0.1375536000
_diffrn_orient_matrix_UB_32      0.0058038000
_diffrn_orient_matrix_UB_33      -0.0189375000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1038
_diffrn_reflns_av_unetI/netI     0.0748
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            37557
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.026
_diffrn_reflns_theta_min         3.497
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.396
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65516
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
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    1.312
_exptl_crystal_description       needle
_exptl_crystal_F_000             1488
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.155
_refine_diff_density_min         -0.553
_refine_diff_density_rms         0.072
_refine_ls_abs_structure_details
;
 Flack x determined using 2073 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.332(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     445
_refine_ls_number_reflns         7487
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0824
_refine_ls_R_factor_gt           0.0616
_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^)+(0.0723P)^2^+2.2629P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1462
_refine_ls_wR_factor_ref         0.1606
_reflns_Friedel_coverage         0.778
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.976
_reflns_number_gt                5883
_reflns_number_total             7487
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ob01679f2.cif
_cod_data_source_block           shhk_210208_3
_cod_database_code               7158920
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.890
_shelx_estimated_absorpt_t_min   0.715
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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 Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B), C14(H14A,H14B), C15(H15A,H15B)
2.b Aromatic/amide H refined with riding coordinates:
 N35(H35), C19(H19), C23(H23), C49(H49), C5(H5), C22(H22), C21(H21), C24(H24),
 C2(H2), C20(H20), C4(H4), C32(H32), C33(H33), C29(H29), C48(H48), C31(H31),
 C30(H30), C45(H45), C46(H46), C47(H47)
2.c Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C), C41(H41A,H41B,H41C), C40(H40A,H40B,H40C)
;
_shelx_res_checksum              74509
_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 1.724
_oxdiff_exptl_absorpt_empirical_full_min 0.654