Regiocontrol in the oxidative Heck reaction of indole by ligand-enabled switch of the regioselectivity-determining step
Wang, Yu-Jie; Yuan, Chen-Hui; Chu, De-Zhao; Jiao, Lei; Chemical Science  (2020) –; doi:10.1039/D0SC02246B

data_1559170
_publ_section_title
;
 Regiocontrol in the oxidative Heck reaction of indole by ligand-enabled
 switch of the regioselectivity-determining step
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC02246B
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C16 H19 Cl2 N O2 Pd S, C H Cl3'
_chemical_formula_sum            'C17 H20 Cl5 N O2 Pd S'
_chemical_formula_weight         586.05
_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             2019-11-22
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_audit_update_record
;
2020-01-17 deposited with the CCDC.	2020-09-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 115.259(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.65140(10)
_cell_length_b                   16.4017(2)
_cell_length_c                   8.71580(10)
_cell_measurement_reflns_used    7009
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      74.6950
_cell_measurement_theta_min      5.3970
_cell_volume                     1118.50(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2137
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_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    -90.00 -57.00   1.00    1.00    --  -40.81 125.00 120.00   33
  2  \w   -111.00 -16.00   1.00    1.00    --  -40.81 -57.00 -90.00   95
  3  \w    -64.00  32.00   1.00    1.00    --  -40.81  38.00-150.00   96
  4  \w    -63.00  27.00   1.00    1.00    --  -40.81  57.00  60.00   90
  5  \w     87.00 138.00   1.00    1.00    --  107.77  61.00   0.00   51
  6  \w     75.00 115.00   1.00    1.00    --  107.77-125.00-150.00   40
  7  \w     73.00 103.00   1.00    1.00    --  107.77 -95.00-120.00   30
  8  \w    102.00 166.00   1.00    1.00    --  107.77  45.00-150.00   64
  9  \w     36.00 124.00   1.00    1.00    --  107.77 -61.00 -90.00   88
 10  \w     38.00 132.00   1.00    1.00    --  107.77 -45.00  30.00   94
 11  \w     83.00 156.00   1.00    1.00    --  107.77  77.00-120.00   73
 12  \w     57.00 169.00   1.00    1.00    --  107.77  15.00   0.00  112
 13  \w     36.00 130.00   1.00    1.00    --  107.77 -61.00 150.00   94
 14  \w     77.00 117.00   1.00    1.00    --  107.77-125.00  30.00   40
 15  \w     58.00  83.00   1.00    1.00    --  107.77-125.00-180.00   25
 16  \w     29.00 109.00   1.00    1.00    --  107.77 -95.00  60.00   80
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1808997000
_diffrn_orient_matrix_UB_12      -0.0124124000
_diffrn_orient_matrix_UB_13      -0.0108792000
_diffrn_orient_matrix_UB_21      0.0751096000
_diffrn_orient_matrix_UB_22      -0.0053685000
_diffrn_orient_matrix_UB_23      0.1949288000
_diffrn_orient_matrix_UB_31      -0.0197818000
_diffrn_orient_matrix_UB_32      0.0929329000
_diffrn_orient_matrix_UB_33      0.0098644000
_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  0.0301
_diffrn_reflns_av_unetI/netI     0.0318
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            7670
_diffrn_reflns_point_group_measured_fraction_full 0.806
_diffrn_reflns_point_group_measured_fraction_max 0.785
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.597
_diffrn_reflns_theta_min         5.394
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    13.177
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57203
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_density_diffrn    1.740
_exptl_crystal_description       block
_exptl_crystal_F_000             584
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.870
_refine_diff_density_min         -0.876
_refine_diff_density_rms         0.073
_refine_ls_abs_structure_details
;
 Flack x determined using 1229 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.014(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     248
_refine_ls_number_reflns         3604
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0211
_refine_ls_R_factor_gt           0.0211
_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^)+(0.0336P)^2^+0.0649P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0541
_refine_ls_wR_factor_ref         0.0541
_reflns_Friedel_coverage         0.533
_reflns_Friedel_fraction_full    0.597
_reflns_Friedel_fraction_max     0.566
_reflns_number_gt                3596
_reflns_number_total             3604
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc02246b2.cif
_cod_data_source_block           20191122wangyujie-wyj1321
_cod_database_code               1559170
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.79
_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 Ternary CH refined with riding coordinates:
 C00M(H00T)
2.b Secondary CH2 refined with riding coordinates:
 C00I(H00B,H00E)
2.c Aromatic/amide H refined with riding coordinates:
 C00C(H00C), C00D(H00D), C00F(H00F), C00J(H00J), C00L(H00L), C00P(H00P),
 C00Q(H00Q)
2.d Idealised Me refined as rotating group:
 C00N(H00G,H00H,H00I), C00O(H00K,H00M,H00N), C00R(H00O,H00R,H00S)
2.e Idealised tetrahedral OH refined as rotating group:
 O00A(H00A)
;
_shelx_res_checksum              25010
_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 1.680
_oxdiff_exptl_absorpt_empirical_full_min 0.787