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_4135619
_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         'C25 H29 N O4 S Si'
_chemical_formula_sum            'C25 H29 N O4 S Si'
_chemical_formula_weight         467.64
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-07-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.0870(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.30970(10)
_cell_length_b                   14.44160(10)
_cell_length_c                   13.60870(10)
_cell_measurement_reflns_used    40155
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.0640
_cell_measurement_theta_min      4.4270
_cell_volume                     2374.09(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (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_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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    -18.00   8.00   1.00    1.00    --    0.00  38.00-150.00   26
  2  \w    -20.00  23.00   1.00    1.00    --    0.00 -19.00 150.00   43
  3  \w     62.00  88.00   1.00    1.00    --    0.00  57.00-150.00   26
  4  \w     17.00  75.00   1.00    1.00    --    0.00  38.00 -60.00   58
  5  \w    -17.00  84.00   1.00    1.00    --    0.00  77.00   0.00  101
  6  \w     32.00  58.00   1.00    1.00    --    0.00  57.00-150.00   26
  7  \w      5.00  32.00   1.00    1.00    --    0.00 -82.00   0.00   27
  8  \w    -89.00 -49.00   1.00    1.00    --    0.00 -19.00 150.00   40
  9  \w    -19.00   9.00   1.00    1.00    --    0.00  38.00  30.00   28
 10  \w    -83.00 -42.00   1.00    1.00    --    0.00 -82.00   0.00   41
 11  \w     20.00  62.00   1.00    1.00    --    0.00  77.00  90.00   42
 12  \w    -19.00   6.00   1.00    1.00    --    0.00  38.00 -60.00   25
 13  \w    -18.00   7.00   1.00    1.00    --    0.00  57.00-150.00   25
 14  \w     31.00  82.00   1.00    1.00    --    0.00  38.00  30.00   51
 15  \w     26.00  87.00   1.00    1.00    --    0.00  38.00-150.00   61
 16  \w    -28.00   4.00   1.00    1.00    --    0.00  77.00  90.00   32
 17  \w    -88.00 -19.00   1.00    1.00    --    0.00 -57.00-180.00   69
 18  \w     70.00 115.00   1.00    1.00    --   95.80  62.00 155.86   45
 19  \w     71.00 110.00   1.00    1.00    --   95.80  59.00  43.25   39
 20  \w    109.00 183.00   1.00    1.00    --   95.80  76.00 -38.08   74
 21  \w     71.00 183.00   1.00    1.00    --   95.80  62.00  94.32  112
 22  \w     30.00  83.00   1.00    1.00    --   95.80 -82.00-150.00   53
 23  \w      6.00 128.00   1.00    1.00    --   95.80 -82.00  60.00  122
 24  \w    123.00 184.00   1.00    1.00    --   95.80  56.00  75.52   61
 25  \w     87.00 128.00   1.00    1.00    --   95.80 -82.00-150.00   41
 26  \w     71.00 104.00   1.00    1.00    --   95.80  61.00   0.00   33
 27  \w     53.00 126.00   1.00    1.00    --   95.80 -82.00 -60.00   73
 28  \w     65.00  91.00   1.00    1.00    --   95.80  77.00  90.00   26
 29  \w    159.00 184.00   1.00    1.00    --   95.80  77.00  90.00   25
 30  \w     64.00  90.00   1.00    1.00    --   95.80  82.00   0.00   26
 31  \w     65.00  91.00   1.00    1.00    --   95.80  76.00 -38.08   26
 32  \w    121.00 147.00   1.00    1.00    --   95.80  62.00-164.99   26
 33  \w    157.00 184.00   1.00    1.00    --   95.80  45.00  30.00   27
 34  \w     78.00 154.00   1.00    1.00    --   95.80  45.00  30.00   76
 35  \w     73.00 102.00   1.00    1.00    --   95.80  56.00  75.52   29
 36  \w     65.00  90.00   1.00    1.00    --   95.80  77.00   0.00   25
 37  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 120.00   26
 38  \w     66.00  91.00   1.00    1.00    --   95.80  74.00-148.09   25
 39  \w     71.00 183.00   1.00    1.00    --   95.80  59.00 137.43  112
 40  \w     63.00  89.00   1.00    1.00    --   95.80  82.00-150.00   26
 41  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  30.00   25
 42  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -60.00   25
 43  \w     63.00  89.00   1.00    1.00    --   95.80  82.00  90.00   26
 44  \w     63.00  88.00   1.00    1.00    --   95.80  82.00  60.00   25
 45  \w     12.00 127.00   1.00    1.00    --   95.80 -82.00-180.00  115
 46  \w     71.00  97.00   1.00    1.00    --   95.80  61.00-180.00   26
 47  \w     38.00 103.00   1.00    1.00    --   95.80 -61.00  60.00   65
 48  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -30.00   26
 49  \w     63.00  89.00   1.00    1.00    --   95.80  82.00  30.00   26
 50  \w    114.00 183.00   1.00    1.00    --   95.80  82.00  30.00   69
 51  \w     65.00  92.00   1.00    1.00    --   95.80  77.00 -90.00   27
 52  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -30.00   25
 53  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 -60.00   25
 54  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 150.00   25
 55  \w     71.00  97.00   1.00    1.00    --   95.80  61.00-120.00   26
 56  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 150.00   26
 57  \w     99.00 184.00   1.00    1.00    --   95.80  82.00 150.00   85
 58  \w     76.00 118.00   1.00    1.00    --   95.80  30.00  90.00   42
 59  \w     75.00 173.00   1.00    1.00    --   95.80  45.00 -60.00   98
 60  \w    134.00 165.00   1.00    1.00    --   95.80  77.00  52.49   31
 61  \w     63.00  88.00   1.00    1.00    --   95.80  82.00-120.00   25
 62  \w     77.00 185.00   1.00    1.00    --   95.80  45.00-120.00  108
 63  \w     63.00  88.00   1.00    1.00    --   95.80  82.00-180.00   25
 64  \w      9.00  35.00   1.00    1.00    --   95.80 -61.00  60.00   26
 65  \w     92.00 118.00   1.00    1.00    --   95.80 -82.00   0.00   26
 66  \w     37.00  75.00   1.00    1.00    --   95.80 -82.00   0.00   38
 67  \w    126.00 151.00   1.00    1.00    --   95.80  82.00 -90.00   25
 68  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 -90.00   26
 69  \w     66.00  92.00   1.00    1.00    --   95.80  74.00 118.79   26
 70  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  52.49   25
 71  \w     69.00 175.00   1.00    1.00    --   95.80  66.00-111.56  106
 72  \w     70.00 103.00   1.00    1.00    --   95.80  62.00-164.99   33
 73  \w     70.00 140.00   1.00    1.00    --   95.80  62.00 -49.31   70
;
_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      0.0367829000
_diffrn_orient_matrix_UB_12      0.0009760000
_diffrn_orient_matrix_UB_13      -0.1019900000
_diffrn_orient_matrix_UB_21      -0.0333742000
_diffrn_orient_matrix_UB_22      0.1026452000
_diffrn_orient_matrix_UB_23      -0.0136700000
_diffrn_orient_matrix_UB_31      0.1175057000
_diffrn_orient_matrix_UB_32      0.0288603000
_diffrn_orient_matrix_UB_33      0.0521908000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0347
_diffrn_reflns_av_unetI/netI     0.0128
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            54504
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.074
_diffrn_reflns_theta_max         67.074
_diffrn_reflns_theta_min         4.438
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.954
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.20010
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (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    1.308
_exptl_crystal_description       block
_exptl_crystal_F_000             992
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.33
_refine_diff_density_max         0.344
_refine_diff_density_min         -0.336
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     296
_refine_ls_number_reflns         4220
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0312
_refine_ls_R_factor_gt           0.0309
_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^)+(0.0376P)^2^+1.6368P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0786
_refine_ls_wR_factor_ref         0.0788
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4171
_reflns_number_total             4220
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c13012_si_002.cif
_cod_data_source_block           exp_1250
_cod_database_code               4135619
_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, All O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B)
2.b Aromatic/amide H refined with riding coordinates:
 C16(H16), C1(H1), C15(H15), C13(H13), C14(H14), C2(H2), C5(H5), C4(H4A)
2.c Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C20(H20A,H20B,H20C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C7(H7A,H7B,H7C), C25(H25A,H25B,H25C)
2.d Idealised tetrahedral OH refined as rotating group:
 O4(H4)
;
_shelx_res_checksum              93047
_shelx_hkl_checksum              88962
_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 3.864
_oxdiff_exptl_absorpt_empirical_full_min 0.652