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_1567704
_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         'C27 H23 N O2 S'
_chemical_formula_sum            'C27 H23 N O2 S'
_chemical_formula_weight         425.52
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-10-13
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_audit_update_record
;
2022-01-15 deposited with the CCDC.	2022-09-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.298(7)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.4589(6)
_cell_length_b                   9.3504(5)
_cell_length_c                   12.9480(8)
_cell_measurement_reflns_used    3290
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      29.2700
_cell_measurement_theta_min      2.7550
_cell_volume                     1074.06(12)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT n/a (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(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 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    -19.00  42.00   1.00    1.00    --   11.90 -99.00-180.00   61
  2  \w    -15.00  76.00   1.00    1.00    --   11.90  77.00  60.00   91
  3  \w     37.00  75.00   1.00    1.00    --   11.90-138.00 -28.00   38
;
_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      0.0278776000
_diffrn_orient_matrix_UB_12      -0.0030676000
_diffrn_orient_matrix_UB_13      0.0583346000
_diffrn_orient_matrix_UB_21      0.0260749000
_diffrn_orient_matrix_UB_22      0.0714102000
_diffrn_orient_matrix_UB_23      0.0021483000
_diffrn_orient_matrix_UB_31      -0.0702740000
_diffrn_orient_matrix_UB_32      0.0253823000
_diffrn_orient_matrix_UB_33      0.0009446000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0233
_diffrn_reflns_av_unetI/netI     0.0416
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            4686
_diffrn_reflns_point_group_measured_fraction_full 0.808
_diffrn_reflns_point_group_measured_fraction_max 0.808
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.296
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.175
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94537
_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    1.316
_exptl_crystal_description       block
_exptl_crystal_F_000             448
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.219
_refine_diff_density_min         -0.366
_refine_diff_density_rms         0.062
_refine_ls_abs_structure_details
;
 Flack x determined using 957 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.123
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     281
_refine_ls_number_reflns         3047
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.123
_refine_ls_R_factor_all          0.0358
_refine_ls_R_factor_gt           0.0344
_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^)+(0.0327P)^2^+0.2050P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0785
_refine_ls_wR_factor_ref         0.0798
_reflns_Friedel_coverage         0.514
_reflns_Friedel_fraction_full    0.589
_reflns_Friedel_fraction_max     0.589
_reflns_number_gt                2958
_reflns_number_total             3047
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc03524c2.cif
_cod_data_source_block           78-2
_cod_depositor_comments
'Adding full bibliography for 1567702--1567704.cif.'
_cod_database_code               1567704
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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:
 C8(H8), C7(H7)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C18(H18), C3(H3), C22(H22), C20(H20), C16(H16), C25(H25), C11(H11),
 C26(H26), C10(H10), C17(H17), C4(H4), C23(H23), C13(H13), C5(H5), C19(H19),
 C12(H12), C14(H14)
2.c Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C)
;
_shelx_res_checksum              34255
_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 1.251
_oxdiff_exptl_absorpt_empirical_full_min 0.793