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_1576044
_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         'C33 H27 N3 O3'
_chemical_formula_sum            'C33 H27 N3 O3'
_chemical_formula_weight         513.57
_space_group_crystal_system      orthorhombic
_space_group_IT_number           20
_space_group_name_Hall           'C 2c 2'
_space_group_name_H-M_alt        'C 2 2 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-15
_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                90
_cell_formula_units_Z            16
_cell_length_a                   17.8476(5)
_cell_length_b                   27.8909(8)
_cell_length_c                   23.5021(7)
_cell_measurement_reflns_used    9928
_cell_measurement_temperature    151.0
_cell_measurement_theta_max      72.016
_cell_measurement_theta_min      2.939
_cell_volume                     11699.0(6)
_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      151.0
_diffrn_measured_fraction_theta_full 0.971
_diffrn_measured_fraction_theta_max 0.957
_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  0.0732
_diffrn_reflns_av_unetI/netI     0.0449
_diffrn_reflns_Laue_measured_fraction_full 0.971
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            39736
_diffrn_reflns_point_group_measured_fraction_full 0.959
_diffrn_reflns_point_group_measured_fraction_max 0.939
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.038
_diffrn_reflns_theta_min         2.939
_diffrn_source_current           1.1
_diffrn_source_power             0.055
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.604
_exptl_absorpt_correction_T_max  0.7535
_exptl_absorpt_correction_T_min  0.5591
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1449 before and 0.0682 after correction.
The Ratio of minimum to maximum transmission is 0.7420.
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    1.166
_exptl_crystal_description       block
_exptl_crystal_F_000             4320
_exptl_crystal_size_max          0.43
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.32
_refine_diff_density_max         0.132
_refine_diff_density_min         -0.189
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 4102 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.14(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     705
_refine_ls_number_reflns         10831
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0390
_refine_ls_R_factor_gt           0.0349
_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^)+(0.0439P)^2^+0.8273P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0892
_refine_ls_wR_factor_ref         0.0920
_reflns_Friedel_coverage         0.817
_reflns_Friedel_fraction_full    0.946
_reflns_Friedel_fraction_max     0.918
_reflns_number_gt                9953
_reflns_number_total             10831
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06910f2.cif
_cod_data_source_block           18
_cod_depositor_comments
'Adding full bibliography for 1576040--1576044.cif.'
_cod_database_code               1576044
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.830
_shelx_estimated_absorpt_t_min   0.781
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C6(H6), C39(H39)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C38(H38A,H38B)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1), N4(H4), C1(H1A), C2(H2), C3(H3), C11(H11), C13(H13), C14(H14),
 C15(H15), C16(H16), C17(H17), C19(H19), C20(H20), C21(H21), C22(H22), C29(H29),
  C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36),
 C44(H44), C45(H45), C47(H47), C48(H48), C49(H49), C50(H50), C55(H55), C56(H56),
  C57(H57), C58(H58), C59(H59), C61(H61), C62(H62), C63(H63), C64(H64)
2.d X=CH2 refined with riding coordinates:
 C7(H7A,H7B), C24(H24A,H24B)
2.e Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C52(H52A,H52B,H52C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_olex2_submission_special_instructions 'No special instructions were received'