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_4127979
_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         'C32 H24 F N O2 S'
_chemical_formula_sum            'C32 H24 F N O2 S'
_chemical_formula_weight         505.58
_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             2019-01-08
_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                   10.40820(10)
_cell_length_b                   13.61670(10)
_cell_length_c                   18.5933(2)
_cell_measurement_reflns_used    35983
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      68.8810
_cell_measurement_theta_min      2.3580
_cell_volume                     2635.14(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.21a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.21a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.21a (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_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.972
_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     -4.00  50.00   0.50    0.57    --    0.00  37.00   0.00  108
  2  \w     25.00  75.00   0.50    0.57    --    0.00  19.00  60.00  100
  3  \w     41.00  73.00   0.50    0.57    --    0.00  37.00  90.00   64
  4  \w     31.00  64.00   0.50    0.57    --    0.00  57.00 120.00   66
  5  \w     -5.00  25.00   0.50    0.57    --    0.00  37.00  90.00   60
  6  \w    -14.00  22.00   0.50    0.57    --    0.00  19.00  60.00   72
  7  \w     -8.00  17.00   0.50    0.57    --    0.00  57.00 120.00   50
  8  \w    -43.00  -8.00   0.50    0.57    --    0.00 118.00 104.83   70
  9  \w     12.00  39.00   0.50    0.57    --    0.00  85.00 -25.00   54
 10  \w     20.00  73.00   0.50    0.57    --    0.00  77.00 -90.00  106
 11  \w     22.00  67.00   0.50    0.57    --    0.00  19.00-180.00   90
 12  \w     -4.00  21.00   0.50    0.57    --    0.00 -85.00-144.00   50
 13  \w    -12.00  21.00   0.50    0.57    --    0.00  19.00-180.00   66
 14  \w    -11.00  52.00   0.50    0.57    --    0.00  37.00-120.00  126
 15  \w    -11.00  15.00   0.50    0.57    --    0.00 -37.00   0.00   52
 16  \w    -19.00  16.00   0.50    0.57    --    0.00 -25.00 127.38   70
 17  \w    -46.00   5.00   0.50    0.57    --    0.00 -57.00 150.00  102
 18  \w    -70.00 -41.00   0.50    0.57    --    0.00 -25.00 127.38   58
 19  \w    -67.00 -31.00   0.50    0.57    --    0.00 -37.00   0.00   72
 20  \w    -23.00  14.00   0.50    0.57    --    0.00  77.00 -90.00   74
 21  \w    -79.00 -15.00   0.50    2.29    --  -88.50  85.00 -25.00  128
 22  \w    -91.00 -15.00   0.50    2.29    --  -88.50 125.00 120.00  152
 23  \w   -100.00 -74.00   0.50    2.29    --  -88.50 -42.00 -79.80   52
 24  \w    -92.00 -65.00   0.50    2.29    --  -88.50 -78.00-109.61   54
 25  \w    -91.00 -64.00   0.50    2.29    --  -88.50 -78.00-141.49   54
 26  \w    -92.00 -66.00   0.50    2.29    --  -88.50 -73.00 -99.05   52
 27  \w    -88.00 -62.00   0.50    2.29    --  -88.50 -82.00 -37.15   52
 28  \w    -92.00 -66.00   0.50    2.29    --  -88.50 -74.00 -30.96   52
 29  \w    -92.00 -65.00   0.50    2.29    --  -88.50 -76.00  20.32   54
 30  \w    -92.00 -65.00   0.50    2.29    --  -88.50 -76.00  38.17   54
 31  \w    -92.00 -65.00   0.50    2.29    --  -88.50 -76.00 100.19   54
 32  \w    -87.00 -62.00   0.50    2.29    --  -88.50 -82.00 137.65   50
 33  \w    -90.00 -64.00   0.50    2.29    --  -88.50 -78.00 173.33   52
 34  \w    -94.00 -67.00   0.50    2.29    --  -88.50 -71.00 137.04   54
 35  \w    -98.00 -69.00   0.50    2.29    --  -88.50 -65.00 136.23   58
 36  \w    -87.00 -62.00   0.50    2.29    --  -88.50 -82.00 170.18   50
 37  \w    -90.00 -63.00   0.50    2.29    --  -88.50 -80.00 122.53   54
 38  \w    -91.00 -65.00   0.50    2.29    --  -88.50 -77.00  80.72   52
 39  \w    -93.00 -67.00   0.50    2.29    --  -88.50 -71.00  38.31   52
 40  \w    -91.00 -65.00   0.50    2.29    --  -88.50 -77.00  30.00   52
 41  \w    -88.00 -62.00   0.50    2.29    --  -88.50 -82.00  18.77   52
 42  \w    -91.00 -65.00   0.50    2.29    --  -88.50 -75.00   0.08   52
 43  \w    -94.00 -68.00   0.50    2.29    --  -88.50 -68.00 -26.33   52
 44  \w    -87.00 -62.00   0.50    2.29    --  -88.50 -83.00 -62.11   50
 45  \w    -88.00 -63.00   0.50    2.29    --  -88.50 -81.00 -98.17   50
 46  \w    -90.00 -63.00   0.50    2.29    --  -88.50 -80.00-155.07   54
 47  \w    -90.00 -64.00   0.50    2.29    --  -88.50 -78.00-168.64   52
 48  \w    -92.00 -65.00   0.50    2.29    --  -88.50 -76.00-127.95   54
 49  \w    -94.00 -66.00   0.50    2.29    --  -88.50 -74.00 -82.62   56
 50  \w    -97.00 -71.00   0.50    2.29    --  -88.50 -60.00 -78.22   52
 51  \w   -101.00 -75.00   0.50    2.29    --  -88.50 -48.00-121.54   52
 52  \w    -91.00 -65.00   0.50    2.29    --  -88.50 -77.00-150.00   52
 53  \w   -107.00 -73.00   0.50    2.29    --  -88.50 -55.00-145.51   68
 54  \w   -107.00 -73.00   0.50    2.29    --  -88.50 -36.00-129.04   68
 55  \w    -95.00 -69.00   0.50    2.29    --  -88.50 -66.00 -53.90   52
 56  \w    -90.00 -65.00   0.50    2.29    --  -88.50 -77.00   0.00   50
 57  \w    -90.00 -63.00   0.50    2.29    --  -88.50 -81.00  60.86   54
 58  \w    -92.00 -66.00   0.50    2.29    --  -88.50 -73.00 106.17   52
 59  \w    -92.00 -66.00   0.50    2.29    --  -88.50 -73.00  84.35   52
 60  \w    -92.00 -65.00   0.50    2.29    --  -88.50 -76.00  65.01   54
 61  \w    -90.00 -65.00   0.50    2.29    --  -88.50 -77.00  95.12   50
 62  \w    -96.00 -69.00   0.50    2.29    --  -88.50 -68.00 170.61   54
 63  \w   -118.00 -73.00   0.50    2.29    --  -88.50 -37.00 150.00   90
 64  \w   -104.00 -73.00   0.50    2.29    --  -88.50 -52.00  74.61   62
 65  \w   -102.00 -72.00   0.50    2.29    --  -88.50 -51.00  36.76   60
 66  \w   -110.00 -73.00   0.50    2.29    --  -88.50 -46.00 -26.34   74
 67  \w   -104.00 -73.00   0.50    2.29    --  -88.50 -55.00 -34.05   62
 68  \w   -107.00 -73.00   0.50    2.29    --  -88.50 -50.00   6.99   68
 69  \w   -113.00 -73.00   0.50    2.29    --  -88.50 -53.00  16.25   80
 70  \w   -109.00 -74.00   0.50    2.29    --  -88.50 -35.00  34.25   70
 71  \w   -126.00 -71.00   0.50    2.29    --  -88.50 -61.00 -40.34  110
 72  \w   -106.00 -73.00   0.50    2.29    --  -88.50 -50.00 -85.25   66
 73  \w   -121.00 -70.00   0.50    2.29    --  -88.50 -63.00-156.15  102
 74  \w   -135.00-110.00   0.50    2.29    --  -88.50 -85.00-144.00   50
 75  \w   -142.00-112.00   0.50    2.29    --  -88.50 -36.00-129.04   60
 76  \w   -150.00-124.00   0.50    2.29    --  -88.50 -83.00 -62.11   52
 77  \w   -154.00-127.00   0.50    2.29    --  -88.50 -75.00   0.08   54
 78  \w   -158.00-131.00   0.50    2.29    --  -88.50 -74.00 -30.96   54
 79  \w   -160.00-111.00   0.50    2.29    --  -88.50 -82.00 -37.15   98
 80  \w   -150.00-121.00   0.50    2.29    --  -88.50 -76.00  38.17   58
 81  \w   -159.00-134.00   0.50    2.29    --  -88.50 -80.00 122.53   50
 82  \w   -157.00 -73.00   0.50    2.29    --  -88.50 -47.00  92.04  168
 83  \w   -156.00-124.00   0.50    2.29    --  -88.50 -82.00 170.18   64
 84  \w   -158.00-132.00   0.50    2.29    --  -88.50 -82.00 137.65   52
 85  \w   -161.00 -74.00   0.50    2.29    --  -88.50 -41.00 116.08  174
 86  \w   -159.00-106.00   0.50    2.29    --  -88.50 -81.00  60.86  106
 87  \w   -161.00-128.00   0.50    2.29    --  -88.50 -37.00 150.00   66
 88  \w   -159.00-115.00   0.50    2.29    --  -88.50 -66.00 -53.90   88
 89  \w   -158.00 -73.00   0.50    2.29    --  -88.50 -53.00-131.23  170
 90  \w   -160.00-121.00   0.50    2.29    --  -88.50 -80.00-155.07   78
 91  \w   -145.00 -72.00   0.50    2.29    --  -88.50 -57.00-150.00  146
 92  \w     23.00 120.00   0.50    2.29    --   94.32 -85.00-144.00  194
 93  \w     88.00 113.00   0.50    2.29    --   94.32-125.00-180.00   50
 94  \w     62.00 108.00   0.50    2.29    --   94.32 -99.00 -30.00   92
 95  \w     36.00  64.00   0.50    2.29    --   94.32-125.00-180.00   56
 96  \w     32.00  71.00   0.50    2.29    --   94.32-125.00-150.00   78
 97  \w     26.00 111.00   0.50    2.29    --   94.32 -57.00-150.00  170
 98  \w    119.00 144.00   0.50    2.29    --   94.32  85.00 -25.00   50
 99  \w     30.00 107.00   0.50    2.29    --   94.32 -99.00  60.00  154
100  \w     22.00 111.00   0.50    2.29    --   94.32 -77.00  60.00  178
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1470213000
_diffrn_orient_matrix_UB_12      0.0094778000
_diffrn_orient_matrix_UB_13      0.0066080000
_diffrn_orient_matrix_UB_21      -0.0047286000
_diffrn_orient_matrix_UB_22      0.0525971000
_diffrn_orient_matrix_UB_23      -0.0732683000
_diffrn_orient_matrix_UB_31      -0.0163917000
_diffrn_orient_matrix_UB_32      -0.0997224000
_diffrn_orient_matrix_UB_33      -0.0381267000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0437
_diffrn_reflns_av_unetI/netI     0.0146
_diffrn_reflns_Laue_measured_fraction_full 0.972
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            65609
_diffrn_reflns_point_group_measured_fraction_full 0.970
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         66.559
_diffrn_reflns_theta_min         4.024
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.388
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47827
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.21a (Rigaku Oxford Diffraction, 2018)
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    1.274
_exptl_crystal_description       block
_exptl_crystal_F_000             1056
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.136
_refine_diff_density_min         -0.188
_refine_diff_density_rms         0.024
_refine_ls_abs_structure_details
;
 Flack x determined using 1852 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.005(5)
_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     335
_refine_ls_number_reflns         4656
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0328
_refine_ls_R_factor_gt           0.0311
_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^)+(0.0482P)^2^+0.2340P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0862
_refine_ls_wR_factor_ref         0.0877
_reflns_Friedel_coverage         0.760
_reflns_Friedel_fraction_full    0.968
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                4434
_reflns_number_total             4656
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b09303_si_002.cif
_cod_data_source_block           exp_4192
_cod_database_code               4127979
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.934
_shelx_estimated_absorpt_t_min   0.874
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     63.60
_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. Uiso/Uaniso restraints and constraints
Uanis(C24) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3.a Ternary CH refined with riding coordinates:
 C18(H18), C20(H20)
3.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C8(H8), C11(H11), C13(H13), C14(H14),
 C15(H15), C16(H16), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26), C28(H28),
  C29(H29), C31(H31), C32(H32)
3.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_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 5.027
_oxdiff_exptl_absorpt_empirical_full_min 0.561