Asymmetric Friedel-Crafts reaction of unsaturated carbonyl-tethered heteroarenes <i>via</i> vinylogous activation of Pd<sup>0</sup>-π-Lewis base catalysis.
Jiang, Bo; Gui, Wu-Tao; Wang, Hao-Tian; Xie, Ke; Chen, Zhi-Chao; Zhu, Lei; Ouyang, Qin; Du, Wei; Chen, Ying-Chun; Chemical science 14 (2023) 10867–10874; doi:10.1039/d3sc03996j

data_1569906
_publ_section_title
;
 Asymmetric Friedel-Crafts reaction of unsaturated carbonyl-tethered
 heteroarenes <i>via</i> vinylogous activation of
 Pd<sup>0</sup>-&#x3c0;-Lewis base catalysis.
;
_journal_issue                   39
_journal_name_full               'Chemical science'
_journal_page_first              10867
_journal_page_last               10874
_journal_paper_doi               10.1039/d3sc03996j
_journal_volume                  14
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H18.85 N2 O4 S2, C20 H19.574 N2 O4 S2'
_chemical_formula_sum            'C40 H38 N4 O8 S4'
_chemical_formula_weight         830.98
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-07-11
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-03-27 deposited with the CCDC.	2023-09-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.792(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.1003(4)
_cell_length_b                   15.1715(5)
_cell_length_c                   13.9176(5)
_cell_measurement_reflns_used    9964
_cell_measurement_temperature    184(2)
_cell_measurement_theta_max      27.201
_cell_measurement_theta_min      2.459
_cell_volume                     2087.68(13)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      184.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0821
_diffrn_reflns_av_unetI/netI     0.0654
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            37794
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.543
_diffrn_reflns_theta_min         2.009
_diffrn_source_current           1.41
_diffrn_source_power             0.0705
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.283
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6939
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1117 before and 0.0709 after correction.
The Ratio of minimum to maximum transmission is 0.9307.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear reddish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.322
_exptl_crystal_description       block
_exptl_crystal_F_000             868
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.530
_refine_diff_density_min         -0.530
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details
;
 Flack x determined using 2669 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     562
_refine_ls_number_reflns         9567
_refine_ls_number_restraints     38
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0789
_refine_ls_R_factor_gt           0.0537
_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^)+(0.0401P)^2^+1.0088P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1156
_refine_ls_wR_factor_ref         0.1273
_reflns_Friedel_coverage         0.919
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                7247
_reflns_number_total             9567
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc03996j2.cif
_cod_data_source_block           11g
_cod_depositor_comments
'Adding full bibliography for 1569903--1569908.cif.'
_cod_database_code               1569906
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.970
_shelx_estimated_absorpt_t_min   0.900
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H21,H21A,H21B} of C21, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  {H11A,H11B,H11C} of C11, {H41A,H41B,H41C} of C41, {H11D,H11E,H11F} of C11A,
  {H41D,H41E,H41F} of C41A
2. Rigid bond restraints
 C11A, C11
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C3, C3A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 S1, C40
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C11A \\sim C11: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C3 \\sim C3A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
S1 \\sim C40: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
Uanis(C11A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C3) \\sim Ueq, Uanis(C3A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C2A) = Uanis(C2)
4. Others
 Sof(H21A)=Sof(H21B)=Sof(C41A)=Sof(H41D)=Sof(H41E)=Sof(H41F)=1-FVAR(1)
 Sof(H21)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=FVAR(1)
 Sof(N3A)=Sof(H3A)=1-FVAR(2)
 Sof(N3)=Sof(H3)=Sof(H4)=FVAR(2)
 Sof(C3A)=Sof(H3AA)=Sof(H3AB)=1-FVAR(3)
 Sof(C3)=Sof(H3B)=Sof(H3C)=FVAR(3)
 Sof(C11A)=Sof(H11D)=Sof(H11E)=Sof(H11F)=1-FVAR(4)
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=FVAR(4)
 Sof(H12A)=Sof(S1A)=1-FVAR(5)
 Sof(S1)=FVAR(5)
 Sof(H1)=Sof(C2A)=Sof(H2A)=1-FVAR(6)
 Sof(C2)=Sof(H12)=FVAR(6)
5.a Riding coordinates:
 C11A(H11D,H11E,H11F)
5.b Ternary CH refined with riding coordinates:
 C4(H4), C27(H27)
5.c Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C3(H3B,H3C), C3A(H3AA,H3AB)
5.d Aromatic/amide H refined with riding coordinates:
 N7(H7), N4(H4A), N1(H1A), C1(H1), N3(H3), C7(H7A), C8(H8), C12(H12A),
 C12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), C20(H20),
  C21(H21), C23(H23), C24(H24), C29(H29), C30(H30), C31(H31), C32(H32),
 C33(H33), C35(H35), C36(H36), C37(H37), C38(H38), C39(H39), N3A(H3A), C2A(H2A)
5.e Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C41(H41A,H41B,H41C), C41A(H41D,H41E,H41F)
;
_shelx_res_checksum              12309
_olex2_submission_special_instructions 'No special instructions were received'