Enantioselective Synthesis of Atropisomers Featuring Pentatomic Heteroaromatics by Pd-Catalyzed C–H Alkynylation
Zhang, Shuo; Yao, Qi-Jun; Liao, Gang; Li, Xin; Li, Han; Chen, Hao-Ming; Hong, Xin; Shi, Bing-Feng; ACS Catalysis 9 (2019) 1956–; doi:10.1021/acscatal.8b04870

data_4514879
_publ_section_title
;
 Enantioselective Synthesis of Atropisomers Featuring Pentatomic
 Heteroaromatics by Pd-Catalyzed C--H Alkynylation
;
_journal_issue                   3
_journal_name_full               'ACS Catalysis'
_journal_page_first              1956
_journal_paper_doi               10.1021/acscatal.8b04870
_journal_volume                  9
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C32 H33 N O Si'
_chemical_formula_sum            'C32 H33 N O Si'
_chemical_formula_weight         475.68
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-07-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.821(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.3547(3)
_cell_length_b                   43.2835(16)
_cell_length_c                   8.7345(4)
_cell_measurement_reflns_used    5587
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      66.7766
_cell_measurement_theta_min      2.0397
_cell_volume                     2774.3(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_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      296.15
_diffrn_detector_area_resol_mean 10.3592
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_details
;
  1 omega   30.00  117.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       41.5688   38.0000 -150.0000 87

  2 omega  -18.00   50.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       41.5688  -77.0000   30.0000 68

  3 omega    8.00  118.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       41.5688   77.0000   90.0000 110

  4 omega   61.00  154.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000 -150.0000 93

  5 omega   12.00   58.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000 -102.0000 -164.0000 46

  6 omega   95.00  165.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   45.0000  -60.0000 70

  7 omega   23.00   77.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -45.0000   60.0000 54

  8 omega   93.00  137.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000   60.0000 44

  9 omega   35.00   73.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -79.0000  -58.0000 38

 10 omega   96.00  123.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -79.0000  -58.0000 27

 11 omega   60.00   86.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000   60.0000 26

 12 omega   76.00  168.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   45.0000    0.0000 92

 13 omega   60.00  140.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000   90.0000 80

 14 omega   96.00  151.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  125.0000  150.0000 55

 15 omega   19.00  125.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -88.0000   65.0000 106

 16 omega   10.00  129.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -85.0000 -107.0000 119
;
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0094789000
_diffrn_orient_matrix_UB_12      0.0134161000
_diffrn_orient_matrix_UB_13      -0.1625309000
_diffrn_orient_matrix_UB_21      0.0618076000
_diffrn_orient_matrix_UB_22      0.0313218000
_diffrn_orient_matrix_UB_23      0.0692214000
_diffrn_orient_matrix_UB_31      0.2004552000
_diffrn_orient_matrix_UB_32      -0.0103312000
_diffrn_orient_matrix_UB_33      -0.0012916000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0594
_diffrn_reflns_av_unetI/netI     0.0517
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       50
_diffrn_reflns_limit_k_min       -51
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            19344
_diffrn_reflns_point_group_measured_fraction_full 0.969
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        66.888
_diffrn_reflns_theta_max         66.888
_diffrn_reflns_theta_min         2.041
_diffrn_source                   'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.915
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84839
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.139
_exptl_crystal_description       needle
_exptl_crystal_F_000             1016
_exptl_crystal_size_max          0.49
_exptl_crystal_size_mid          0.38
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.785
_refine_diff_density_min         -0.386
_refine_diff_density_rms         0.066
_refine_ls_abs_structure_details
;
 Flack x determined using 2677 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     631
_refine_ls_number_reflns         9556
_refine_ls_number_restraints     153
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.1021
_refine_ls_R_factor_gt           0.0858
_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^)+(0.1950P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2395
_refine_ls_wR_factor_ref         0.2692
_reflns_Friedel_coverage         0.935
_reflns_Friedel_fraction_full    0.950
_reflns_Friedel_fraction_max     0.950
_reflns_number_gt                7300
_reflns_number_total             9556
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b04870_si_002.cif
_cod_data_source_block           180703_zs_2_142_7
_cod_database_code               4514879
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'c h n o si'
_shelx_estimated_absorpt_t_max   0.771
_shelx_estimated_absorpt_t_min   0.663
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_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. Restrained distances
 C56-C58
 1.53 with sigma of 0.02
 C62-C64
 1.53 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C24 \\sim C25 \\sim C26: within 3.8A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C59 \\sim C62 \\sim C56 \\sim C61 \\sim C60 \\sim C64 \\sim C63 \\sim C58 \\sim
C57: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
4.a Ternary CH refined with riding coordinates:
 C27(H27), C24(H24), C59(H59), C30(H30), C62(H62), C56(H56)
4.b Me refined with riding coordinates:
 C25(H25A,H25B,H25C), C28(H28A,H28B,H28C), C31(H31A,H31B,H31C), C29(H29A,H29B,
 H29C), C61(H61A,H61B,H61C), C26(H26A,H26B,H26C), C60(H60A,H60B,H60C), C58(H58A,
 H58B,H58C), C57(H57A,H57B,H57C), C32(H32A,H32B,H32C), C63(H63A,H63B,H63C),
 C64(H64A,H64B,H64C)
4.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C20(H20), C17(H17), C53(H53), C18(H18), C40(H40), C13(H13), C5(H5),
 C52(H52), C12(H12), C21(H21), C44(H44), C45(H45), C51(H51), C4(H4), C37(H37),
 C19(H19), C49(H49), C34(H34), C3(H3), C36(H36), C2(H2), C50(H50), C35(H35)
;
_shelx_res_checksum              73687
_shelx_hkl_checksum              11358
_olex2_submission_special_instructions 'No special instructions were received'