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_1576040
_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 unk
_chemical_formula_moiety         'C30 H26 Cl F2 N O4'
_chemical_formula_sum            'C30 H26 Cl F2 N O4'
_chemical_formula_weight         537.97
_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     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2p3n7q
_audit_creation_date             2024-09-19
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-07-26 deposited with the CCDC.	2025-10-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 113.066(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   15.7945(6)
_cell_length_b                   5.0027(2)
_cell_length_c                   17.3264(6)
_cell_measurement_reflns_used    10502
_cell_measurement_temperature    175(5)
_cell_measurement_theta_max      73.0320
_cell_measurement_theta_min      3.2080
_cell_volume                     1259.60(9)
_computing_cell_refinement       'CrysAlisPro 1.171.42.100a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.100a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.100a (Rigaku OD, 2023)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      175(5)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -86.00 -14.00   1.00    1.00    --    0.00 -57.00  60.00   72
  2  \w     27.00  53.00   1.00    1.00    --    0.00  57.00  30.00   26
  3  \w    -20.00   6.00   1.00    1.00    --    0.00  57.00 -90.00   26
  4  \w    -86.00  -2.00   1.00    1.00    --    0.00 -16.00-163.36   84
  5  \w     28.00  84.00   1.00    1.00    --    0.00  57.00   0.00   56
  6  \w      3.00  70.00   1.00    1.00    --    0.00 -16.00-163.36   67
  7  \w    -27.00  23.00   1.00    1.00    --    0.00  57.00  30.00   50
  8  \w    -26.00   2.00   1.00    1.00    --    0.00  57.00   0.00   28
  9  \w     -5.00  21.00   1.00    1.00    --    0.00 -57.00  60.00   26
 10  \w    -22.00  52.00   1.00    1.00    --    0.00  77.00  60.00   74
 11  \w     47.00  89.00   1.00    1.00    --    0.00  57.00 -90.00   42
 12  \w    -10.00  41.00   1.00    1.00    --    0.00  57.00  60.00   51
 13  \w     79.00 127.00   1.00    1.00    --   92.10 -82.00 -60.00   48
 14  \w     45.00 126.00   1.00    1.00    --   92.10 -82.00 120.00   81
 15  \w    142.00 167.00   1.00    1.00    --   92.10  65.00-168.21   25
 16  \w     58.00  89.00   1.00    1.00    --   92.10  80.00 -89.39   31
 17  \w    146.00 172.00   1.00    1.00    --   92.10  74.00 152.16   26
 18  \w     63.00 102.00   1.00    1.00    --   92.10  65.00-168.21   39
 19  \w     66.00 182.00   1.00    1.00    --   92.10  44.00  68.40  116
 20  \w     59.00  91.00   1.00    1.00    --   92.10  77.00 -30.00   32
 21  \w     59.00  85.00   1.00    1.00    --   92.10  77.00 120.00   26
 22  \w     60.00  86.00   1.00    1.00    --   92.10  74.00 152.16   26
 23  \w     66.00 103.00   1.00    1.00    --   92.10  45.00 -60.00   37
 24  \w    129.00 175.00   1.00    1.00    --   92.10  45.00 -60.00   46
 25  \w      4.00 120.00   1.00    1.00    --   92.10 -61.00  90.00  116
 26  \w     57.00  85.00   1.00    1.00    --   92.10  82.00 -60.00   28
 27  \w     57.00  83.00   1.00    1.00    --   92.10  82.00  90.00   26
 28  \w    109.00 179.00   1.00    1.00    --   92.10  82.00  90.00   70
 29  \w     57.00  91.00   1.00    1.00    --   92.10  82.00 150.00   34
 30  \w     64.00  90.00   1.00    1.00    --   92.10  61.00-120.00   26
 31  \w    127.00 153.00   1.00    1.00    --   92.10  82.00-150.00   26
 32  \w     57.00  82.00   1.00    1.00    --   92.10  82.00-150.00   25
 33  \w     58.00  84.00   1.00    1.00    --   92.10  79.00  -1.28   26
 34  \w     59.00  85.00   1.00    1.00    --   92.10  76.00  28.17   26
 35  \w     57.00  83.00   1.00    1.00    --   92.10  82.00 120.00   26
 36  \w     60.00  86.00   1.00    1.00    --   92.10  82.00 -30.00   26
 37  \w     57.00 114.00   1.00    1.00    --   92.10 -82.00  30.00   57
 38  \w     59.00  85.00   1.00    1.00    --   92.10  82.00-120.00   26
 39  \w     60.00  85.00   1.00    1.00    --   92.10  77.00 -60.00   25
 40  \w    117.00 179.00   1.00    1.00    --   92.10  82.00-180.00   62
 41  \w     66.00  92.00   1.00    1.00    --   92.10  45.00-120.00   26
 42  \w     66.00 118.00   1.00    1.00    --   92.10  52.00-116.86   52
 43  \w     60.00  86.00   1.00    1.00    --   92.10  77.00 -90.00   26
 44  \w     60.00  85.00   1.00    1.00    --   92.10  77.00  30.00   25
 45  \w    122.00 148.00   1.00    1.00    --   92.10  77.00  30.00   26
 46  \w     59.00 103.00   1.00    1.00    --   92.10  77.00  60.00   44
 47  \w      4.00 128.00   1.00    1.00    --   92.10 -82.00-150.00  124
 48  \w    100.00 177.00   1.00    1.00    --   92.10  63.00 106.36   77
 49  \w     66.00 164.00   1.00    1.00    --   92.10  45.00 -30.00   98
 50  \w     67.00 134.00   1.00    1.00    --   92.10  45.00   0.00   67
 51  \w    140.00 179.00   1.00    1.00    --   92.10  45.00   0.00   39
 52  \w     67.00  93.00   1.00    1.00    --   92.10  45.00  30.00   26
 53  \w     68.00  95.00   1.00    1.00    --   92.10  61.00 120.00   27
 54  \w    143.00 182.00   1.00    1.00    --   92.10  61.00 120.00   39
 55  \w     57.00  88.00   1.00    1.00    --   92.10  82.00-180.00   31
 56  \w     99.00 124.00   1.00    1.00    --   92.10 -77.00-120.00   25
 57  \w     64.00  90.00   1.00    1.00    --   92.10  82.00  60.00   26
 58  \w      7.00  78.00   1.00    1.00    --   92.10 -77.00-120.00   71
 59  \w    129.00 175.00   1.00    1.00    --   92.10  48.00 157.56   46
 60  \w     66.00  94.00   1.00    1.00    --   92.10  48.00 157.56   28
 61  \w     68.00 126.00   1.00    1.00    --   92.10  45.00-180.00   58
 62  \w    130.00 156.00   1.00    1.00    --   92.10  45.00-180.00   26
 63  \w    136.00 182.00   1.00    1.00    --   92.10  61.00-120.00   46
 64  \w     59.00  98.00   1.00    1.00    --   92.10  77.00-120.00   39
 65  \w     67.00  93.00   1.00    1.00    --   92.10  49.00  35.46   26
 66  \w     64.00  90.00   1.00    1.00    --   92.10  63.00 106.36   26
 67  \w     66.00  93.00   1.00    1.00    --   92.10  50.00  65.43   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0522013000
_diffrn_orient_matrix_UB_12      -0.0519976000
_diffrn_orient_matrix_UB_13      -0.0945239000
_diffrn_orient_matrix_UB_21      -0.0203061000
_diffrn_orient_matrix_UB_22      0.3014605000
_diffrn_orient_matrix_UB_23      -0.0146516000
_diffrn_orient_matrix_UB_31      0.0899284000
_diffrn_orient_matrix_UB_32      0.0375627000
_diffrn_orient_matrix_UB_33      -0.0135972000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0703
_diffrn_reflns_av_unetI/netI     0.0487
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            23076
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.073
_diffrn_reflns_theta_max         67.073
_diffrn_reflns_theta_min         3.214
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.800
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.08334
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.100a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_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    1.418
_exptl_crystal_description       block
_exptl_crystal_F_000             560
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.234
_refine_diff_density_min         -0.230
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 1418 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.019(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     345
_refine_ls_number_reflns         4449
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0458
_refine_ls_R_factor_gt           0.0390
_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^)+(0.0524P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0942
_refine_ls_wR_factor_ref         0.0984
_reflns_Friedel_coverage         0.774
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                3879
_reflns_number_total             4449
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06910f2.cif
_cod_data_source_block           exp_4465_auto
_cod_depositor_comments
'Adding full bibliography for 1576040--1576044.cif.'
_cod_database_code               1576040
_shelx_shelxl_version_number     2018/3
_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.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C13(H13A,H13B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C9(H9), C10(H10), C16(H16), C18(H18),
 C19(H19), C25(H25), C26(H26), C28(H28), C29(H29)
2.c Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C30(H30A,H30B,H30C)
;
_shelx_res_checksum              48853
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 10.046
_oxdiff_exptl_absorpt_empirical_full_min 0.478