Palladium-catalyzed redox diversified entry to axially chiral styrenes <i>via</i> asymmetric olefination with alkynes.
Lin, Ziwei; Jiang, Yuqing; Wang, Fen; Huang, Genping; Li, Jessica; Li, Xingwei; Chemical science 16 (2025) 14252–14261; doi:10.1039/d5sc04080a

data_1575049
_publ_section_title
;
 Palladium-catalyzed redox diversified entry to axially chiral styrenes
 <i>via</i> asymmetric olefination with alkynes.
;
_journal_issue                   31
_journal_name_full               'Chemical science'
_journal_page_first              14252
_journal_page_last               14261
_journal_paper_doi               10.1039/d5sc04080a
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration rmad
_chemical_formula_moiety         '4(C38 H33 N O5 S)'
_chemical_formula_sum            'C152 H132 N4 O20 S4'
_chemical_formula_weight         2462.85
_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     iterative
_audit_block_doi                 10.5517/ccdc.csd.cc2m3v0m
_audit_creation_date             2024-04-28
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-01-14 deposited with the CCDC.	2025-07-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.905(4)
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   9.8872(12)
_cell_length_b                   31.082(4)
_cell_length_c                   11.0103(14)
_cell_measurement_reflns_used    9573
_cell_measurement_temperature    243.00
_cell_measurement_theta_max      68.361
_cell_measurement_theta_min      4.245
_cell_volume                     3201.1(7)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      243.00
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0309
_diffrn_reflns_av_unetI/netI     0.0308
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            55156
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.511
_diffrn_reflns_theta_min         2.843
_diffrn_source_current           50.0
_diffrn_source_power             2.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.262
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6436
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0703 before and 0.0601 after correction.
The Ratio of minimum to maximum transmission is 0.8546.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.278
_exptl_crystal_description       block
_exptl_crystal_F_000             1296
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.175
_refine_diff_density_min         -0.857
_refine_diff_density_rms         0.077
_refine_ls_abs_structure_details
;
 Flack x determined using 5201 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.064(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.995
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     744
_refine_ls_number_reflns         11558
_refine_ls_number_restraints     219
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.0906
_refine_ls_R_factor_gt           0.0895
_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^)+(0.1974P)^2^+2.1363P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2533
_refine_ls_wR_factor_ref         0.2551
_reflns_Friedel_coverage         0.943
_reflns_Friedel_fraction_full    0.975
_reflns_Friedel_fraction_max     0.970
_reflns_number_gt                11261
_reflns_number_total             11558
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc04080a2.cif
_cod_data_source_block           a_a_CCDC1
_cod_depositor_comments
'Adding full bibliography for 1575048--1575050.cif.'
_cod_database_code               1575049
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.906
_shelx_estimated_absorpt_t_min   0.863
_olex2_refinement_description
;
1. Restrained distances
 C40-O3 = O3-C39
 1.39 with sigma of 0.02
 C40-C39
 2.408 with sigma of 0.04
2. Uiso/Uaniso restraints and constraints
C72 \\sim C73 \\sim C74 \\sim C75 \\sim C77 \\sim C78: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C53 \\sim O10 \\sim C50 \\sim C49 \\sim C48 \\sim C43 \\sim C44 \\sim C45 \\sim
C46 \\sim C47 \\sim C52 \\sim C51: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C72 \\sim C73 \\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C75 \\sim C77 \\sim C78 \\sim C72 \\sim C74 \\sim C73 \\sim C76: within 2A with
sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C1: within 2A with sigma
of 0.001 and sigma for terminal atoms of 0.002 within 2A
Uanis(C40) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C78) \\sim Ueq, Uanis(C77) \\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C73)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C2) \\sim Ueq, Uanis(C7) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C72) \\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C77)
\\sim Ueq, Uanis(C78) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
3. Others
 Fixed Y: S1(0.24037)
4.a Secondary CH2 refined with riding coordinates:
 C63(H63A,H63B), C9(H9A,H9B), C62(H62A,H62B), C8(H8A,H8B)
4.b Aromatic/amide H refined with riding coordinates:
 C55(H55), C54(H54), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25),
 C56(H56), C78(H78), C77(H77), C74(H74), C73(H73), C58(H58), C65(H65), C12(H12),
  C49(H49), C67(H67), C68(H68), C69(H69), C70(H70), C71(H71), C14(H14),
 C15(H15), C57(H57), C51(H51), C18(H18), C46(H46), C7(H7), C6(H6), C4(H4),
 C3(H3), C45(H45), C52(H52), C17(H17), C34(H34), C33(H33), C30(H30), C36(H36),
 C37(H37), C16(H16)
4.c Fitted hexagon refined as free rotating group:
 C21(C22,C23,C24,C25,C20), C72(C78,C77,C75,C74,C73), C67(C68,C69,C70,C71,C66),
 C2(C7,C6,C5,C4,C3)
4.d Naphthalene refined as free rotating group:
 C34(C33,C31,C30,C29,C35,C36,C37,C38,C28)
4.e Idealised Me refined as rotating group:
 C41(H41A,H41B,H41C), C76(H76A,H76B,H76C), C53(H53A,H53B,H53C), C1(H1A,H1B,
 H1C), C32(H32A,H32B,H32C), C40(H40A,H40B,H40C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              70581
_shelx_fab_checksum              46708
_olex2_submission_special_instructions 'No special instructions were received'