Pd(ii)-catalyzed enantioselective C-H olefination and photoregulation of sterically hindered diarylethenes.
Zhang, Guanlun; Wu, Xu; Mao, Shiyu; Li, Mengqi; Hu, Honglong; Shi, Bing-Feng; Zhu, Wei-Hong; Chemical science 15 (2024) 20013–20021; doi:10.1039/d4sc05375c

data_1573074
_publ_section_title
;
 Pd(ii)-catalyzed enantioselective C-H olefination and photoregulation of
 sterically hindered diarylethenes.
;
_journal_issue                   47
_journal_name_full               'Chemical science'
_journal_page_first              20013
_journal_page_last               20021
_journal_paper_doi               10.1039/d4sc05375c
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C19 H14 N4 O2 S4'
_chemical_formula_sum            'C19 H14 N4 O2 S4'
_chemical_formula_weight         458.58
_chemical_name_systematic        8
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-05-21
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-05-31 deposited with the CCDC.	2024-11-03 downloaded from the CCDC.
;
_cell_angle_alpha                97.434(2)
_cell_angle_beta                 92.683(2)
_cell_angle_gamma                90.008(2)
_cell_formula_units_Z            4
_cell_length_a                   7.7696(4)
_cell_length_b                   15.7256(8)
_cell_length_c                   19.9214(10)
_cell_measurement_reflns_used    9906
_cell_measurement_temperature    170.00
_cell_measurement_theta_max      54.83
_cell_measurement_theta_min      2.94
_cell_volume                     2410.9(2)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      170.00
_diffrn_measured_fraction_theta_full 0.980
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_unetI/netI     0.0828
_diffrn_reflns_Laue_measured_fraction_full 0.980
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            8958
_diffrn_reflns_point_group_measured_fraction_full 0.490
_diffrn_reflns_point_group_measured_fraction_max 0.488
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         54.876
_diffrn_reflns_theta_min         2.465
_diffrn_source_current           2.85
_diffrn_source_power             0.19887300000000002
_diffrn_source_voltage           69.78
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.505
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.5502
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.1497 before and 0.0791 after correction.
 
For component 2:
 wR2(int) was 0.1598 before and 0.0823 after correction.
 The Ratio of minimum to maximum transmission is 0.55.

Final HKLF 4 output contains 51294 reflections, Rint = 0.1087
 (23458 with I > 3sig(I), Rint = 0.0866)
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.263
_exptl_crystal_description       block
_exptl_crystal_F_000             944
_exptl_crystal_recrystallization_method 'Vapour deposition'
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.396
_refine_diff_density_min         -0.705
_refine_diff_density_rms         0.084
_refine_ls_abs_structure_details
;
No quotients, so Flack parameter determined by classical intensity fit
;
_refine_ls_abs_structure_Flack   0.02(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1065
_refine_ls_number_reflns         8958
_refine_ls_number_restraints     33
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0936
_refine_ls_R_factor_gt           0.0665
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1298P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1691
_refine_ls_wR_factor_ref         0.1890
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    0.000
_reflns_Friedel_fraction_max     0.000
_reflns_number_gt                6667
_reflns_number_total             8958
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05375c2.cif
_cod_data_source_block           mj24480_0m_4
_cod_depositor_comments          'Adding full bibliography for 1573074.cif.'
_cod_database_code               1573074
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.885
_shelx_estimated_absorpt_t_min   0.675
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5933(17)
 0.4067(17)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(C3A) \\sim Ueq, Uanis(C3B) \\sim Ueq, Uanis(C021) \\sim Ueq, Uanis(C14C)
\\sim Ueq, Uanis(C11) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
4.a Aromatic/amide H refined with riding coordinates:
 C10(H10), C10A(H10A), C10B(H10B), C10C(H10C)
4.b Tetrahedral OH refined with riding coordinates:
 O2(H2)
4.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C12(H12A,H12B,H12C), C15(H15A,H15B,H15C), C18(H18A,H18B,
 H18C), C9A(H9AA,H9AB,H9AC), C12A(H12D,H12E,H12F), C15A(H15D,H15E,H15F),
 C18A(H18D,H18E,H18F), C9B(H9BA,H9BB,H9BC), C12B(H12G,H12H,H12I), C15B(H15G,
 H15H,H15I), C18B(H18G,H18H,H18I), C9C(H9CA,H9CB,H9CC), C12C(H12J,H12K,H12L),
 C15C(H15J,H15K,H15L), C18C(H18J,H18K,H18L)
4.d Idealised tetrahedral OH refined as rotating group:
 O1A(H1A), O2B(H2B), O1C(H1C)
;
_shelx_res_checksum              60543
_shelx_hkl_checksum              44547
_shelx_fab_checksum              63233
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'