Palladium-catalysed asymmetric annulations of Morita-Baylis-Hillman carbonates with allenes or alkenes <i>via</i> migratory insertion.
Huang, Jin-Yu; Qin, Xin-Ting; Rao, Han-Wen; Chen, Zhi-Chao; Zhu, Lei; Ouyang, Qin; Du, Wei; Chen, Ying-Chun; Chemical science 16 (2025) 22456–22464; doi:10.1039/d5sc06910f

data_1576042
_publ_section_title
;
 Palladium-catalysed asymmetric annulations of Morita-Baylis-Hillman
 carbonates with allenes or alkenes <i>via</i> migratory insertion.
;
_journal_issue                   47
_journal_name_full               'Chemical science'
_journal_page_first              22456
_journal_page_last               22464
_journal_paper_doi               10.1039/d5sc06910f
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C30 H25 N O6 S'
_chemical_formula_sum            'C30 H25 N O6 S'
_chemical_formula_weight         527.57
_space_group_crystal_system      trigonal
_space_group_IT_number           145
_space_group_name_Hall           'P 32'
_space_group_name_H-M_alt        'P 32'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-04-09
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-07-16 deposited with the CCDC.	2025-10-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   16.834(5)
_cell_length_b                   16.834(5)
_cell_length_c                   8.235(3)
_cell_measurement_reflns_used    5170
_cell_measurement_temperature    302(2)
_cell_measurement_theta_max      27.238
_cell_measurement_theta_min      2.420
_cell_volume                     2021.0(11)
_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      302.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_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  0.0842
_diffrn_reflns_av_unetI/netI     0.0990
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            16041
_diffrn_reflns_point_group_measured_fraction_full 0.966
_diffrn_reflns_point_group_measured_fraction_max 0.950
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.647
_diffrn_reflns_theta_min         2.420
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.164
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.4717
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1516 before and 0.0928 after correction.
The Ratio of minimum to maximum transmission is 0.6326.
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    1.300
_exptl_crystal_description       needle
_exptl_crystal_F_000             828
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.350
_refine_diff_density_min         -0.265
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 1471 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     356
_refine_ls_number_reflns         5967
_refine_ls_number_restraints     19
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0795
_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^)+(0.0234P)^2^+0.1381P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1122
_refine_ls_wR_factor_ref         0.1281
_reflns_Friedel_coverage         0.913
_reflns_Friedel_fraction_full    0.932
_reflns_Friedel_fraction_max     0.907
_reflns_number_gt                4448
_reflns_number_total             5967
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06910f2.cif
_cod_data_source_block           4e
_cod_depositor_comments
'Adding full bibliography for 1576040--1576044.cif.'
_cod_original_cell_volume        2021.1(14)
_cod_database_code               1576042
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.992
_shelx_estimated_absorpt_t_min   0.945
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C10A, C10
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C10 \\sim C10A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
Uanis(C10A) \\sim Ueq, Uanis(C10) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Sof(H9BC)=Sof(H9BD)=Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=1-FVAR(1)
 Sof(H9AA)=Sof(H9AB)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C6(H6)
5.b Secondary CH2 refined with riding coordinates:
 C9(H9AA,H9AB), C9(H9BC,H9BD)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C29(H29), C11(H11), C12(H12), C14(H14), C15(H15), C16(H16), C17(H17),
 C18(H18), C21(H21), C25(H25), C26(H26), C27(H27), C28(H28)
5.d X=CH2 refined with riding coordinates:
 C20(H20A,H20B)
5.e Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C10(H10A,H10B,H10C), C10A(H10D,H10E,H10F)
;
_shelx_res_checksum              97411
_olex2_submission_special_instructions 'No special instructions were received'