Palladium-catalysed asymmetric cascade transformations of 4-alken-2-ynyl carbonates to construct complex frameworks.
He, Ze-Liang; Li, Li; Chen, Zhi-Chao; Du, Wei; Chen, Ying-Chun; Chemical science 16 (2025) 3124–3129; doi:10.1039/d4sc07823c

data_1574056
_publ_section_title
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 Palladium-catalysed asymmetric cascade transformations of 4-alken-2-ynyl
 carbonates to construct complex frameworks.
;
_journal_issue                   7
_journal_name_full               'Chemical science'
_journal_page_first              3124
_journal_page_last               3129
_journal_paper_doi               10.1039/d4sc07823c
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C36 H32 N2 O3 S'
_chemical_formula_sum            'C36 H32 N2 O3 S'
_chemical_formula_weight         572.69
_space_group_crystal_system      tetragonal
_space_group_IT_number           96
_space_group_name_Hall           'P 4nw 2abw'
_space_group_name_H-M_alt        'P 43 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-05-27
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-09-01 deposited with the CCDC.	2025-01-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   12.4257(6)
_cell_length_b                   12.4257(6)
_cell_length_c                   42.988(4)
_cell_measurement_reflns_used    6118
_cell_measurement_temperature    303(2)
_cell_measurement_theta_max      21.945
_cell_measurement_theta_min      2.318
_cell_volume                     6637.3(8)
_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      303.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_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  0.0566
_diffrn_reflns_av_unetI/netI     0.0770
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -55
_diffrn_reflns_number            22897
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.447
_diffrn_reflns_theta_min         1.893
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.133
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6781
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0768 before and 0.0551 after correction.
The Ratio of minimum to maximum transmission is 0.9095.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.146
_exptl_crystal_description       block
_exptl_crystal_F_000             2416
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.42
_exptl_crystal_size_min          0.26
_refine_diff_density_max         0.144
_refine_diff_density_min         -0.215
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 1165 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.985
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     381
_refine_ls_number_reflns         7524
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      0.985
_refine_ls_R_factor_all          0.1202
_refine_ls_R_factor_gt           0.0542
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0530P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1043
_refine_ls_wR_factor_ref         0.1296
_reflns_Friedel_coverage         0.710
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.990
_reflns_number_gt                4097
_reflns_number_total             7524
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07823c2.cif
_cod_data_source_block           12g
_cod_original_cell_volume        6637.3(9)
_cod_database_code               1574056
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.966
_shelx_estimated_absorpt_t_min   0.939
_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
2. Rigid bond restraints
 S1, O3
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
O3 \\sim S1: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
4.a Ternary CH refined with riding coordinates:
 C6(H6), C7(H7)
4.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C18(H18A,H18B)
4.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C9(H9), C10(H10), C11(H11), C13(H13), C14(H14), C15(H15),
 C16(H16), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25), C30(H30),
  C31(H31), C32(H32)
4.d X=CH2 refined with riding coordinates:
 C36(H36A,H36B)
4.e Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C28(H28A,H28B,H28C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 196 electrons were 
found in a volume of 1000\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
1[n-Hexane] per Asymmetric Unit 
which account for 4 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              26084
_shelx_fab_checksum              535
_olex2_submission_special_instructions 'No special instructions were received'