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_4135618
_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         'C34 H36 N2 O6 S2 Si'
_chemical_formula_sum            'C34 H36 N2 O6 S2 Si'
_chemical_formula_weight         660.86
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-10-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                103.4620(10)
_cell_angle_beta                 90.2360(10)
_cell_angle_gamma                104.924(2)
_cell_formula_units_Z            2
_cell_length_a                   6.86330(10)
_cell_length_b                   11.6049(2)
_cell_length_c                   24.2941(4)
_cell_measurement_reflns_used    23018
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.3670
_cell_measurement_theta_min      4.8080
_cell_volume                     1814.10(5)
_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 0.992
_diffrn_measured_fraction_theta_max 0.979
_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      6.00  82.00   1.00    1.00    --    0.00  82.00 120.00   76
  2  \w    -12.00  30.00   1.00    1.00    --    0.00  38.00 150.00   42
  3  \w    -23.00  79.00   1.00    1.00    --    0.00  19.00 -60.00  102
  4  \w    -31.00  -6.00   1.00    1.00    --    0.00  82.00 120.00   25
  5  \w     58.00  84.00   1.00    1.00    --    0.00  57.00  90.00   26
  6  \w    -29.00  14.00   1.00    1.00    --    0.00  77.00-120.00   43
  7  \w     43.00  80.00   1.00    1.00    --    0.00  38.00   0.00   37
  8  \w    -14.00  22.00   1.00    1.00    --    0.00  38.00  30.00   36
  9  \w     20.00  62.00   1.00    1.00    --    0.00  77.00-120.00   42
 10  \w    -75.00 -32.00   1.00    1.00    --    0.00 -57.00 120.00   43
 11  \w     36.00  80.00   1.00    1.00    --    0.00  38.00 150.00   44
 12  \w    -19.00  27.00   1.00    1.00    --    0.00  38.00   0.00   46
 13  \w    -22.00  53.00   1.00    1.00    --    0.00  57.00  90.00   75
 14  \w     43.00  71.00   1.00    1.00    --    0.00  38.00  30.00   28
 15  \w     -9.00  20.00   1.00    1.00    --    0.00 -57.00 120.00   29
 16  \w     41.00 120.00   1.00    1.00    --   95.80 -61.00 -30.00   79
 17  \w     10.00  37.00   1.00    1.00    --   95.80 -61.00 -30.00   27
 18  \w     63.00  90.00   1.00    1.00    --   95.80  82.00   4.95   27
 19  \w    145.00 185.00   1.00    1.00    --   95.80  71.00  48.22   40
 20  \w     67.00  93.00   1.00    1.00    --   95.80  71.00  48.22   26
 21  \w     70.00 175.00   1.00    1.00    --   95.80  66.00-171.40  105
 22  \w    112.00 170.00   1.00    1.00    --   95.80  82.00-134.00   58
 23  \w     71.00  96.00   1.00    1.00    --   95.80  61.00   0.00   25
 24  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -90.00   26
 25  \w     28.00  54.00   1.00    1.00    --   95.80 -82.00  90.00   26
 26  \w     58.00 116.00   1.00    1.00    --   95.80 -82.00  90.00   58
 27  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 150.00   25
 28  \w    106.00 132.00   1.00    1.00    --   95.80  82.00 150.00   26
 29  \w      6.00 124.00   1.00    1.00    --   95.80 -82.00 -90.00  118
 30  \w     63.00  89.00   1.00    1.00    --   95.80  82.00-150.00   26
 31  \w     63.00  89.00   1.00    1.00    --   95.80  82.00  60.00   26
 32  \w     65.00 139.00   1.00    1.00    --   95.80  77.00-150.00   74
 33  \w     68.00 167.00   1.00    1.00    --   95.80  68.00 150.64   99
 34  \w     65.00  92.00   1.00    1.00    --   95.80  77.00  90.00   27
 35  \w     61.00 123.00   1.00    1.00    --   95.80 -82.00 -30.00   62
 36  \w     64.00  89.00   1.00    1.00    --   95.80  80.00-165.94   25
 37  \w     65.00  91.00   1.00    1.00    --   95.80  76.00 114.43   26
 38  \w     71.00 183.00   1.00    1.00    --   95.80  61.00 120.00  112
 39  \w      8.00 110.00   1.00    1.00    --   95.80 -61.00 150.00  102
 40  \w     65.00  91.00   1.00    1.00    --   95.80  77.00-180.00   26
 41  \w     63.00  95.00   1.00    1.00    --   95.80  82.00 -60.00   32
 42  \w     71.00  96.00   1.00    1.00    --   95.80  61.00 -60.00   25
 43  \w     12.00  51.00   1.00    1.00    --   95.80 -82.00 -30.00   39
 44  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -30.00   25
 45  \w     65.00  90.00   1.00    1.00    --   95.80  77.00   0.00   25
 46  \w     75.00 109.00   1.00    1.00    --   95.80  45.00 -60.00   34
 47  \w    119.00 148.00   1.00    1.00    --   95.80  45.00 -60.00   29
 48  \w     75.00 140.00   1.00    1.00    --   95.80  45.00 120.00   65
 49  \w     65.00  90.00   1.00    1.00    --   95.80  82.00 -90.00   25
 50  \w     77.00 116.00   1.00    1.00    --   95.80  45.00 -30.00   39
 51  \w     76.00 162.00   1.00    1.00    --   95.80  45.00  30.00   86
 52  \w     75.00 178.00   1.00    1.00    --   95.80  45.00  60.00  103
 53  \w    119.00 184.00   1.00    1.00    --   95.80  82.00-120.00   65
 54  \w    113.00 138.00   1.00    1.00    --   95.80  77.00 -60.00   25
 55  \w    133.00 159.00   1.00    1.00    --   95.80  69.00 -20.07   26
 56  \w     63.00  88.00   1.00    1.00    --   95.80  82.00-120.00   25
 57  \w     65.00 116.00   1.00    1.00    --   95.80  77.00  60.00   51
 58  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 120.00   26
 59  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 -60.00   25
 60  \w     71.00 145.00   1.00    1.00    --   95.80  61.00-180.00   74
 61  \w     75.00 178.00   1.00    1.00    --   95.80  45.00   0.00  103
 62  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  30.00   25
 63  \w     21.00 117.00   1.00    1.00    --   95.80 -82.00 150.00   96
 64  \w     68.00  93.00   1.00    1.00    --   95.80  69.00 -20.07   25
 65  \w     68.00  94.00   1.00    1.00    --   95.80  70.00-159.73   26
 66  \w     63.00  99.00   1.00    1.00    --   95.80  82.00-134.00   36
 67  \w     75.00 101.00   1.00    1.00    --   95.80  47.00 -75.73   26
;
_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      0.0067533000
_diffrn_orient_matrix_UB_12      -0.0649449000
_diffrn_orient_matrix_UB_13      0.0482533000
_diffrn_orient_matrix_UB_21      -0.0537996000
_diffrn_orient_matrix_UB_22      -0.1253530000
_diffrn_orient_matrix_UB_23      -0.0434904000
_diffrn_orient_matrix_UB_31      0.2264415000
_diffrn_orient_matrix_UB_32      0.0108544000
_diffrn_orient_matrix_UB_33      -0.0071897000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0484
_diffrn_reflns_av_unetI/netI     0.0311
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            43298
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.471
_diffrn_reflns_theta_min         3.750
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.002
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.33462
_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    1.210
_exptl_crystal_description       block
_exptl_crystal_F_000             696
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.276
_refine_diff_density_min         -0.438
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     414
_refine_ls_number_reflns         7293
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0365
_refine_ls_R_factor_gt           0.0345
_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^)+(0.0374P)^2^+0.9339P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0883
_refine_ls_wR_factor_ref         0.0895
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6762
_reflns_number_total             7293
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c13012_si_003.cif
_cod_data_source_block           exp_1010
_cod_database_code               4135618
_shelx_shelxl_version_number     2016/6
_reflns_odcompleteness_completeness 99.54
_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, All O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B)
2.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13), C16(H16), C17(H17), C19(H19),
 C20(H20), C23(H23), C24(H24), C26(H26), C27(H27)
2.c Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C)
2.d Idealised tetrahedral OH refined as rotating group:
 O6(H6)
;
_shelx_res_checksum              31358
_shelx_hkl_checksum              51442
_shelx_fab_checksum              76228
_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 2.098
_oxdiff_exptl_absorpt_empirical_full_min 0.432