Palladium-catalyzed intramolecular enantioselective C(sp3)–H insertion of donor/donor carbenes
Li, Wendeng; Zhang, He; Chen, Kai; Jiang, Huanfeng; Sun, Jianwei; Zhu, Shifa; Chemical Science 13 (2022) 12396–12402; doi:10.1039/D2SC03524C

data_1567703
_publ_section_title
;
 Palladium-catalyzed intramolecular enantioselective C(sp3)--H insertion
 of donor/donor carbenes
;
_journal_issue                   42
_journal_name_full               'Chemical Science'
_journal_page_first              12396
_journal_page_last               12402
_journal_paper_doi               10.1039/D2SC03524C
_journal_volume                  13
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C28 H25 N O2 S'
_chemical_formula_sum            'C28 H25 N O2 S'
_chemical_formula_weight         439.55
_space_group_crystal_system      trigonal
_space_group_IT_number           144
_space_group_name_Hall           'P 31'
_space_group_name_H-M_alt        'P 31'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-01-09
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.09.11 svn.r3730fd0d for OlexSys, GUI svn.r6159)
;
_audit_update_record
;
2022-01-15 deposited with the CCDC.	2022-09-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   10.2503(2)
_cell_length_b                   10.2503(2)
_cell_length_c                   18.6428(4)
_cell_measurement_reflns_used    8622
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.7170
_cell_measurement_theta_min      2.3440
_cell_volume                     1696.35(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.984
_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   -115.00 -77.00   1.00    1.00    --  -40.73 -38.00  30.00   38
  2  \w    -67.00 -19.00   1.00    1.00    --  -40.73 -57.00 120.00   48
  3  \w   -114.00 -88.00   1.00    1.00    --  -40.73-149.00 -19.00   26
  4  \w    -51.00 -16.00   1.00    1.00    --  -40.73 -38.00 -30.00   35
  5  \w   -114.00 -57.00   1.00    1.00    --  -40.73 -38.00 -30.00   57
  6  \w    -46.00 -17.00   1.00    1.00    --  -40.73 -38.00  30.00   29
  7  \w     12.00  37.00   1.00    1.00    --   40.73  77.00 120.00   25
  8  \w     18.00  45.00   1.00    1.00    --   40.73  38.00  90.00   27
  9  \w     60.00  92.00   1.00    1.00    --   40.73-125.00-120.00   32
 10  \w     12.00  51.00   1.00    1.00    --   40.73-110.00  14.00   39
 11  \w    124.00 150.00   1.00    1.00    --  107.58  61.00 120.00   26
 12  \w     83.00 110.00   1.00    1.00    --  107.58  45.00  90.00   27
 13  \w     75.00 101.00   1.00    1.00    --  107.58  77.00  90.00   26
 14  \w     75.00 101.00   1.00    1.00    --  107.58  77.00 120.00   26
 15  \w     79.00 106.00   1.00    1.00    --  107.58  61.00 150.00   27
 16  \w     78.00 104.00   1.00    1.00    --  107.58  61.00 120.00   26
 17  \w     25.00  95.00   1.00    1.00    --  107.58 -94.00-180.00   70
 18  \w     78.00 108.00   1.00    1.00    --  107.58  61.00  90.00   30
 19  \w     79.00 106.00   1.00    1.00    --  107.58  61.00  60.00   27
 20  \w    136.00 178.00   1.00    1.00    --  107.58 125.00-120.00   42
 21  \w     83.00 143.00   1.00    1.00    --  107.58  45.00 120.00   60
 22  \w     82.00 128.00   1.00    1.00    --  107.58  45.00 150.00   46
 23  \w    135.00 170.00   1.00    1.00    --  107.58  45.00 150.00   35
 24  \w     36.00 130.00   1.00    1.00    --  107.58 -45.00 -90.00   94
 25  \w    112.00 177.00   1.00    1.00    --  107.58  77.00  60.00   65
 26  \w     75.00 102.00   1.00    1.00    --  107.58  77.00  60.00   27
 27  \w     80.00 117.00   1.00    1.00    --  107.58  30.00  90.00   37
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1721129000
_diffrn_orient_matrix_UB_12      0.0947619000
_diffrn_orient_matrix_UB_13      0.0097350000
_diffrn_orient_matrix_UB_21      0.0155014000
_diffrn_orient_matrix_UB_22      -0.1354263000
_diffrn_orient_matrix_UB_23      -0.0240694000
_diffrn_orient_matrix_UB_31      0.0165591000
_diffrn_orient_matrix_UB_32      0.0532920000
_diffrn_orient_matrix_UB_33      -0.0783995000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0271
_diffrn_reflns_av_unetI/netI     0.0294
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            10380
_diffrn_reflns_point_group_measured_fraction_full 0.970
_diffrn_reflns_point_group_measured_fraction_max 0.939
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.006
_diffrn_reflns_theta_min         4.982
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.465
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58803
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.291
_exptl_crystal_description       block
_exptl_crystal_F_000             696
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.189
_refine_diff_density_min         -0.210
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 1958 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.006(8)
_refine_ls_extinction_coef       0.0057(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     292
_refine_ls_number_reflns         4315
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0303
_refine_ls_R_factor_gt           0.0299
_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^)+(0.0541P)^2^+0.0969P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0819
_refine_ls_wR_factor_ref         0.0828
_reflns_Friedel_coverage         0.908
_reflns_Friedel_fraction_full    0.941
_reflns_Friedel_fraction_max     0.894
_reflns_number_gt                4258
_reflns_number_total             4315
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc03524c2.cif
_cod_data_source_block           17-3
_cod_depositor_comments
'Adding full bibliography for 1567702--1567704.cif.'
_cod_original_cell_volume        1696.35(8)
_cod_database_code               1567703
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Ternary CH refined with riding coordinates:
 C2(H2)
2.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C10(H10), C11(H11), C12(H12), C13(H13),
 C14(H14), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C23(H23), C24(H24),
  C26(H26), C27(H27)
2.c Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C)
;
_shelx_res_checksum              84515
_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 1.639
_oxdiff_exptl_absorpt_empirical_full_min 0.473