Rh(I)-Catalyzed Carbene Migration/Carbonylation/Cyclization: Straightforward Construction of Fully Substituted Aryne Precursors.
Zhu, Guohao; Gao, Wen-Chao; Jiang, Xuefeng; Journal of the American Chemical Society 143 (2021) 1334–1340; doi:10.1021/jacs.0c13012

data_4135620
_publ_section_title
;
 Rh(I)-Catalyzed Carbene Migration/Carbonylation/Cyclization:
 Straightforward Construction of Fully Substituted Aryne Precursors.
;
_journal_issue                   3
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              1334
_journal_page_last               1340
_journal_paper_doi               10.1021/jacs.0c13012
_journal_volume                  143
_journal_year                    2021
_chemical_formula_moiety         'C39 H27 N O4 S, C3 H7 N O'
_chemical_formula_sum            'C42 H34 N2 O5 S'
_chemical_formula_weight         678.77
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-07-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.3220(10)
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   10.74330(10)
_cell_length_b                   45.1666(4)
_cell_length_c                   21.5283(2)
_cell_measurement_reflns_used    95550
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.3690
_cell_measurement_theta_min      3.5790
_cell_volume                     10243.06(17)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_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_measured_fraction_theta_full 1.000
_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     20.00  58.00   1.00    1.00    --    0.00  57.00-150.00   38
  2  \w     58.00  87.00   1.00    1.00    --    0.00  38.00 150.00   29
  3  \w    -86.00 -34.00   1.00    1.00    --    0.00 -38.00  60.00   52
  4  \w     20.00  56.00   1.00    1.00    --    0.00  38.00 150.00   36
  5  \w     -7.00  19.00   1.00    1.00    --    0.00 -38.00  60.00   26
  6  \w     -2.00  29.00   1.00    1.00    --    0.00 -77.00 -30.00   31
  7  \w    -60.00 -17.00   1.00    1.00    --    0.00 -77.00 -30.00   43
  8  \w    -23.00  17.00   1.00    1.00    --    0.00  57.00  90.00   40
  9  \w    -19.00  70.00   1.00    1.00    --    0.00  38.00   0.00   89
 10  \w    -18.00  11.00   1.00    1.00    --    0.00  38.00 150.00   29
 11  \w    -21.00   6.00   1.00    1.00    --    0.00  57.00-150.00   27
 12  \w    -77.00  24.00   1.00    1.00    --    0.00 -19.00-150.00  101
 13  \w     57.00  88.00   1.00    1.00    --    0.00  57.00  90.00   31
 14  \w    -86.00  23.00   1.00    1.00    --    0.00 -57.00   0.00  109
 15  \w    135.00 161.00   1.00    1.00    --   95.80  74.00 -66.46   26
 16  \w     66.00  99.00   1.00    1.00    --   95.80  74.00 -66.46   33
 17  \w    116.00 159.00   1.00    1.00    --   95.80  63.00-135.85   43
 18  \w     66.00  91.00   1.00    1.00    --   95.80  74.00  -0.40   25
 19  \w     63.00  89.00   1.00    1.00    --   95.80  81.00-134.62   26
 20  \w     70.00  98.00   1.00    1.00    --   95.80  63.00-135.85   28
 21  \w     65.00 124.00   1.00    1.00    --   95.80  76.00-101.84   59
 22  \w     16.00  71.00   1.00    1.00    --   95.80 -82.00 120.00   55
 23  \w     75.00 113.00   1.00    1.00    --   95.80 -82.00 120.00   38
 24  \w     72.00 157.00   1.00    1.00    --   95.80  61.00 150.00   85
 25  \w     71.00 104.00   1.00    1.00    --   95.80  61.00   0.00   33
 26  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -90.00   25
 27  \w      6.00 125.00   1.00    1.00    --   95.80 -77.00  60.00  119
 28  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  90.00   25
 29  \w     65.00 102.00   1.00    1.00    --   95.80  77.00 150.00   37
 30  \w    143.00 185.00   1.00    1.00    --   95.80  45.00   0.00   42
 31  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 120.00   26
 32  \w     67.00 185.00   1.00    1.00    --   95.80  73.00  55.15  118
 33  \w     63.00  89.00   1.00    1.00    --   95.80  82.00   0.00   26
 34  \w    135.00 163.00   1.00    1.00    --   95.80  81.00 159.91   28
 35  \w     68.00  95.00   1.00    1.00    --   95.80  70.00  49.21   27
 36  \w     70.00 184.00   1.00    1.00    --   95.80  66.00  92.93  114
 37  \w    100.00 169.00   1.00    1.00    --   95.80  75.00  74.45   69
 38  \w     66.00  91.00   1.00    1.00    --   95.80  75.00  74.45   25
 39  \w     63.00 130.00   1.00    1.00    --   95.80  81.00 159.91   67
 40  \w     53.00 128.00   1.00    1.00    --   95.80 -82.00-150.00   75
 41  \w     63.00  88.00   1.00    1.00    --   95.80  82.00-120.00   25
 42  \w     65.00  91.00   1.00    1.00    --   95.80  77.00  30.00   26
 43  \w     64.00  99.00   1.00    1.00    --   95.80  79.00 171.97   35
 44  \w    141.00 166.00   1.00    1.00    --   95.80  82.00 120.00   25
 45  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 -30.00   25
 46  \w     65.00 103.00   1.00    1.00    --   95.80  77.00-120.00   38
 47  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -30.00   25
 48  \w    129.00 184.00   1.00    1.00    --   95.80  81.00 107.23   55
 49  \w     63.00  89.00   1.00    1.00    --   95.80  82.00  90.00   26
 50  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 150.00   26
 51  \w     65.00  90.00   1.00    1.00    --   95.80  77.00-150.00   25
 52  \w     65.00 145.00   1.00    1.00    --   95.80  77.00 -90.00   80
 53  \w    150.00 177.00   1.00    1.00    --   95.80  77.00 -90.00   27
 54  \w     65.00  91.00   1.00    1.00    --   95.80  77.00  60.00   26
 55  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 -60.00   26
 56  \w    111.00 184.00   1.00    1.00    --   95.80  68.00 -26.13   73
 57  \w    142.00 171.00   1.00    1.00    --   95.80  61.00-150.00   29
 58  \w     66.00  91.00   1.00    1.00    --   95.80  77.00 120.00   25
 59  \w     63.00  89.00   1.00    1.00    --   95.80  82.00-150.00   26
 60  \w     75.00 118.00   1.00    1.00    --   95.80  45.00   0.00   43
 61  \w     63.00  88.00   1.00    1.00    --   95.80  82.00-180.00   25
 62  \w     13.00 127.00   1.00    1.00    --   95.80 -82.00  30.00  114
 63  \w     71.00 138.00   1.00    1.00    --   95.80  61.00-150.00   67
 64  \w     75.00 185.00   1.00    1.00    --   95.80  44.00-100.85  110
 65  \w     68.00  94.00   1.00    1.00    --   95.80  68.00 -26.13   26
 66  \w     71.00 109.00   1.00    1.00    --   95.80  61.00  30.00   38
 67  \w    119.00 144.00   1.00    1.00    --   95.80  61.00  30.00   25
 68  \w     71.00  96.00   1.00    1.00    --   95.80  61.00 120.00   25
 69  \w     10.00 128.00   1.00    1.00    --   95.80 -82.00-120.00  118
 70  \w     63.00 124.00   1.00    1.00    --   95.80 -82.00 -60.00   61
 71  \w     63.00  88.00   1.00    1.00    --   95.80  81.00 107.23   25
 72  \w    156.00 181.00   1.00    1.00    --   95.80  76.00-101.84   25
 73  \w     69.00 182.00   1.00    1.00    --   95.80  67.00 -49.90  113
 74  \w     69.00 162.00   1.00    1.00    --   95.80  65.00  37.11   93
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0639240000
_diffrn_orient_matrix_UB_12      0.0248643000
_diffrn_orient_matrix_UB_13      -0.0439336000
_diffrn_orient_matrix_UB_21      0.0160825000
_diffrn_orient_matrix_UB_22      -0.0183350000
_diffrn_orient_matrix_UB_23      -0.0582634000
_diffrn_orient_matrix_UB_31      -0.1305467000
_diffrn_orient_matrix_UB_32      -0.0144456000
_diffrn_orient_matrix_UB_33      -0.0017308000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0649
_diffrn_reflns_av_unetI/netI     0.0251
_diffrn_reflns_Laue_measured_fraction_full 1.000
_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       53
_diffrn_reflns_limit_k_min       -53
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            260268
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.078
_diffrn_reflns_theta_max         67.078
_diffrn_reflns_theta_min         2.865
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.246
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.37929
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
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    1.320
_exptl_crystal_description       block
_exptl_crystal_F_000             4272
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.16
_refine_diff_density_max         1.015
_refine_diff_density_min         -0.748
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.183
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1360
_refine_ls_number_reflns         18287
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.183
_refine_ls_R_factor_all          0.0799
_refine_ls_R_factor_gt           0.0765
_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^)+(0.0384P)^2^+32.1899P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1770
_refine_ls_wR_factor_ref         0.1787
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17215
_reflns_number_total             18287
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c13012_si_004.cif
_cod_data_source_block           exp_1251
_cod_depositor_comments
;

2025-07-29
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_moiety     '3(C39 H27 N O4 S), 3(C3 H7 N O)'
_cod_original_formula_sum        'C126 H102 N6 O15 S3'
_cod_original_formula_units_Z    4
_cod_original_formula_weight     2036.31
_cod_database_code               4135620
_shelx_shelxl_version_number     2017/1
_reflns_odcompleteness_completeness 99.98
_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 Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C42(H42A,H42B), C81(H81A,H81B)
2.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C14(H14), C15(H15), C16(H16), C17(H17),
 C22(H22), C23(H23), C25(H25), C26(H26), C28(H28), C29(H29), C30(H30), C31(H31),
  C32(H32), C34(H34), C35(H35), C36(H36), C37(H37), C38(H38), C47(H47),
 C48(H48), C49(H49), C50(H50), C55(H55), C56(H56), C57(H57), C58(H58), C61(H61),
  C62(H62), C63(H63), C64(H64), C65(H65), C67(H67), C68(H68), C69(H69),
 C70(H70), C71(H71), C73(H73), C74(H74), C76(H76), C77(H77), C86(H86), C87(H87),
  C88(H88), C89(H89), C94(H94), C95(H95), C96(H96), C97(H97), C100(H100),
 C101(H101), C102(H102), C103(H103), C104(H104), C106(H106), C107(H107),
 C108(H108), C109(H109), C110(H110), C112(H112), C113(H113), C115(H115),
 C116(H116), C118(H118), C122(H122), C124(H124)
2.c Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C), C78(H78A,H78B,H78C), C117(H11A,H11B,H11C), C119(H11D,
 H11E,H11F), C120(H12A,H12B,H12C), C121(H12D,H12E,H12F), C123(H12G,H12H,H12I),
 C125(H12J,H12K,H12L), C126(H12M,H12N,H12O)
;
_shelx_res_checksum              85111
_shelx_hkl_checksum              91922
_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 3.030
_oxdiff_exptl_absorpt_empirical_full_min 0.725