Generation of Donor/Donor Copper Carbenes through Copper-Catalyzed Diyne Cyclization: Enantioselective and Divergent Synthesis of Chiral Polycyclic Pyrroles.
Hong, Feng-Lin; Wang, Ze-Shu; Wei, Dong-Dong; Zhai, Tong-Yi; Deng, Guo-Cheng; Lu, Xin; Liu, Rai-Shung; Ye, Long-Wu; Journal of the American Chemical Society 141 (2019) 16961–16970; doi:10.1021/jacs.9b09303

data_4127980
_publ_section_title
;
 Generation of Donor/Donor Copper Carbenes through Copper-Catalyzed Diyne
 Cyclization: Enantioselective and Divergent Synthesis of Chiral
 Polycyclic Pyrroles.
;
_journal_issue                   42
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              16961
_journal_page_last               16970
_journal_paper_doi               10.1021/jacs.9b09303
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C24 H18 Br N O3 S'
_chemical_formula_sum            'C24 H18 Br N O3 S'
_chemical_formula_weight         480.36
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2019-04-09
_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            4
_cell_length_a                   5.4770(2)
_cell_length_b                   17.2742(5)
_cell_length_c                   22.0070(6)
_cell_measurement_reflns_used    4660
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      61.6080
_cell_measurement_theta_min      3.2540
_cell_volume                     2082.10(11)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1903
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.878
_diffrn_measured_fraction_theta_max 1.000
_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  39.00   1.00    8.00    --  -32.31  38.00 -30.00  101
  2  \w   -109.00 -60.00   1.00    8.00    --  -32.31-178.00 -90.00   49
  3  \w     10.00 103.00   1.00    8.00    --   32.31  57.00-180.00   93
  4  \w    -36.00  56.00   1.00    8.00    --   32.31 -57.00  30.00   92
  5  \w     57.00  85.00   1.00    8.00    --   32.31 158.00-160.00   28
  6  \w     23.00  77.00   1.00    8.00    --   32.31 -99.00 -90.00   54
  7  \w    -12.00  14.00   1.00    8.00    --   32.31 -99.00 -90.00   26
  8  \w     60.00 116.00   1.00   19.50    --   94.50 -64.00  30.00   56
  9  \w    130.00 157.00   1.00   19.50    --   94.50  64.00-150.00   27
 10  \w     22.00  59.00   1.00   19.50    --   94.50-112.00  30.00   37
 11  \w     25.00  88.00   1.00   19.50    --   94.50 -64.00 150.00   63
 12  \w    128.00 155.00   1.00   19.50    --   94.50  12.00 -30.00   27
 13  \w     95.00 127.00   1.00   19.50    --   94.50 -25.00-150.00   32
 14  \w     25.00  52.00   1.00   19.50    --   94.50 -50.00  30.00   27
 15  \w     72.00  99.00   1.00   19.50    --   94.50  64.00-150.00   27
 16  \w     25.00 102.00   1.00   19.50    --   94.50 -64.00-150.00   77
 17  \w     26.00  53.00   1.00   19.50    --   94.50-112.00  60.00   27
 18  \w     33.00 136.00   1.00   19.50    --   94.50 -92.00  30.00  103
 19  \w    107.00 133.00   1.00   19.50    --   94.50  38.00 120.00   26
 20  \w     93.00 136.00   1.00   19.50    --   94.50  64.00   0.00   43
 21  \w     78.00 105.00   1.00   19.50    --   94.50 -92.00 120.00   27
 22  \w     22.00  70.00   1.00   19.50    --   94.50 -77.00 -30.00   48
 23  \w     20.00 134.00   1.00   19.50    --   94.50 -25.00   0.00  114
 24  \w     22.00 106.00   1.00   19.50    --   94.50  12.00 -30.00   84
 25  \w     51.00 101.00   1.00   19.50    --   94.50 -92.00 -60.00   50
 26  \w     39.00  76.00   1.00   19.50    --   94.50 -25.00-150.00   37
 27  \w     72.00  99.00   1.00   19.50    --   94.50 -92.00-150.00   27
 28  \w     78.00 119.00   1.00   19.50    --   94.50  50.00-150.00   41
 29  \w     46.00  71.00   1.00   19.50    --   94.50 -92.00-150.00   25
 30  \w     76.00 119.00   1.00   19.50    --   94.50 -50.00  30.00   43
 31  \w     26.00  67.00   1.00   19.50    --   94.50-112.00  90.00   41
 32  \w     87.00 163.00   1.00   19.50    --   94.50  38.00-180.00   76
 33  \w    136.00 165.00   1.00   19.50    --   94.50  64.00  90.00   29
 34  \w    138.00 165.00   1.00   19.50    --   94.50  50.00-120.00   27
 35  \w     31.00  88.00   1.00   19.50    --   94.50 -64.00-120.00   57
 36  \w     60.00  85.00   1.00   19.50    --   94.50 -64.00 -30.00   25
 37  \w     29.00  56.00   1.00   19.50    --   94.50 -92.00  60.00   27
 38  \w     56.00 114.00   1.00   19.50    --   94.50 -93.00-177.54   58
 39  \w    102.00 128.00   1.00   15.00    --   94.50 178.00   0.00   26
 40  \w     72.00  98.00   1.00   15.00    --   94.50  38.00 -60.00   26
 41  \w    103.00 129.00   1.00   15.00    --   94.50  38.00 -60.00   26
 42  \w    103.00 128.00   1.00   15.00    --   94.50 -77.00  30.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0389928000
_diffrn_orient_matrix_UB_12      0.0031686000
_diffrn_orient_matrix_UB_13      -0.0692793000
_diffrn_orient_matrix_UB_21      -0.1553737000
_diffrn_orient_matrix_UB_22      0.0742072000
_diffrn_orient_matrix_UB_23      -0.0032985000
_diffrn_orient_matrix_UB_31      0.2312183000
_diffrn_orient_matrix_UB_32      0.0493688000
_diffrn_orient_matrix_UB_33      0.0094528000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0776
_diffrn_reflns_av_unetI/netI     0.0491
_diffrn_reflns_Laue_measured_fraction_full 0.878
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            16569
_diffrn_reflns_point_group_measured_fraction_full 0.872
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.684
_diffrn_reflns_theta_min         3.252
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.847
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67630
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.532
_exptl_crystal_description       block
_exptl_crystal_F_000             976
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.665
_refine_diff_density_min         -0.471
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Flack x determined using 1190 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.027(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     272
_refine_ls_number_reflns         3290
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0448
_refine_ls_R_factor_gt           0.0420
_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^)+(0.0636P)^2^+0.2954P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1114
_refine_ls_wR_factor_ref         0.1163
_reflns_Friedel_coverage         0.695
_reflns_Friedel_fraction_full    0.864
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                3066
_reflns_number_total             3290
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b09303_si_003.cif
_cod_data_source_block           exp_20422
_cod_database_code               4127980
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 88.60
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C13(H13)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C7(H7), C10(H10), C14(H14), C15(H15),
 C16(H16), C17(H17), C19(H19), C20(H20), C22(H22), C23(H23)
2.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C)
;
_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 1.964
_oxdiff_exptl_absorpt_empirical_full_min 0.490