Regioselective Synthesis of Spirocyclic Pyrrolines via a Palladium-Catalyzed Narasaka-Heck/C-H Activation/[4+2] Annulation Cascade Reaction
Wei, Wan-Xu; Kong, Xiangtao; Jiao, Rui-Qiang; Li, Xue-Song; Wang, Cui-Tian; Li, Yuke; Liang, Yong-Min; Chemical Science  (2022) –; doi:10.1039/D2SC01887J

data_1566930
_publ_section_title
;
 Regioselective Synthesis of Spirocyclic Pyrrolines via a
 Palladium-Catalyzed Narasaka-Heck/C-H Activation/[4+2] Annulation Cascade
 Reaction
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC01887J
_journal_year                    2022
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C27 H27 N O2'
_chemical_formula_sum            'C27 H27 N O2'
_chemical_formula_weight         397.49
_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_creation_date             2021-10-13
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2021-11-25 deposited with the CCDC.	2022-05-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.225(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.6464(2)
_cell_length_b                   23.7748(6)
_cell_length_c                   10.1622(3)
_cell_measurement_reflns_used    8143
_cell_measurement_temperature    296(9)
_cell_measurement_theta_max      76.3030
_cell_measurement_theta_min      3.7270
_cell_volume                     2157.46(11)
_computing_cell_refinement       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      296(9)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.945
_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    112.00 175.00   0.50    0.18    --  107.75  57.00-180.00  126
  2  \w    103.00 128.00   0.50    0.18    --  107.75 119.00-153.00   50
  3  \w     60.00  89.00   0.50    0.05    --   47.57 155.00   3.00   58
  4  \w     94.00 166.00   0.50    0.18    --  107.75  57.00 120.00  144
  5  \w     36.00 106.00   0.50    0.18    --  107.75 -99.00 120.00  140
  6  \w     73.00 102.00   0.50    0.18    --  107.75-119.00 121.00   58
  7  \w     68.00 113.00   0.50    0.05    --   47.57-155.00 -34.00   90
  8  \w     82.00 131.00   0.50    0.18    --  107.75-155.00 -34.00   98
  9  \w     35.00  77.00   0.50    0.18    --  107.75-155.00 -34.00   84
 10  \w     35.00  60.00   0.50    0.05    --   47.57-119.00 121.00   50
 11  \w     37.00  63.00   0.50    0.18    --  107.75 -57.00   0.00   52
 12  \w    -11.00  21.00   0.50    0.05    --   47.57 -19.00 -60.00   64
 13  \w    -26.00  23.00   0.50    0.05    --   47.57 -19.00 -90.00   98
 14  \w    -24.00   6.00   0.50    0.05    --   47.57 -19.00-120.00   60
 15  \w    -26.00  23.00   0.50    0.05    --   47.57 -19.00-180.00   98
 16  \w    -92.00 -67.00   0.50    0.18    -- -100.00 119.00-153.00   50
 17  \w    -91.00 -28.00   0.50    0.18    -- -100.00 125.00-120.00  126
 18  \w   -109.00 -84.00   0.50    0.18    -- -100.00 155.00   3.00   50
 19  \w   -111.00 -63.00   0.50    0.18    -- -100.00 125.00 150.00   96
 20  \w    -52.00 -27.00   0.50    0.18    -- -100.00 125.00 150.00   50
 21  \w    -29.00  20.00   0.50    0.05    --  -47.57  19.00 120.00   98
 22  \w    -67.00 -39.00   0.50    0.18    -- -100.00  57.00  30.00   56
 23  \w    -69.00 -38.00   0.50    0.18    -- -100.00  57.00-120.00   62
 24  \w    -68.00 -30.00   0.50    0.18    -- -100.00  57.00-150.00   76
 25  \w   -153.00 -84.00   0.50    0.18    -- -100.00-125.00  30.00  138
 26  \w   -162.00 -62.00   0.50    0.18    -- -100.00-155.00 -34.00  200
 27  \w   -115.00 -90.00   0.50    0.05    --  -47.57-155.00 -34.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0315879000
_diffrn_orient_matrix_UB_12      0.0619440000
_diffrn_orient_matrix_UB_13      0.0234901000
_diffrn_orient_matrix_UB_21      -0.0440245000
_diffrn_orient_matrix_UB_22      -0.0176393000
_diffrn_orient_matrix_UB_23      0.1247979000
_diffrn_orient_matrix_UB_31      0.1638103000
_diffrn_orient_matrix_UB_32      0.0071795000
_diffrn_orient_matrix_UB_33      0.1034166000
_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  0.0868
_diffrn_reflns_av_unetI/netI     0.0894
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.945
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            16761
_diffrn_reflns_point_group_measured_fraction_full 0.871
_diffrn_reflns_point_group_measured_fraction_max 0.807
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.573
_diffrn_reflns_theta_min         3.718
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.598
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58231
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.113a (Rigaku Oxford Diffraction, 2021)
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    1.224
_exptl_crystal_description       block
_exptl_crystal_F_000             848
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.687
_refine_diff_density_min         -0.452
_refine_diff_density_rms         0.106
_refine_ls_abs_structure_details
;
 Flack x determined using 1985 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.4(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.007
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     549
_refine_ls_number_reflns         7398
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.007
_refine_ls_R_factor_all          0.1021
_refine_ls_R_factor_gt           0.0888
_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^)+(0.1905P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2268
_refine_ls_wR_factor_ref         0.2496
_reflns_Friedel_coverage         0.667
_reflns_Friedel_fraction_full    0.739
_reflns_Friedel_fraction_max     0.662
_reflns_number_gt                5823
_reflns_number_total             7398
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc01887j2.cif
_cod_data_source_block           weiwanxu_1013-1_auto
_cod_depositor_comments
;

2025-06-02
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C54 H54 N2 O4'
_cod_original_formula_weight         794.99
_cod_original_formula_moiety         '2(C27 H27 N O2)'
_cod_original_formula_units_Z            2
_cod_original_cell_volume        2157.46(10)
_cod_database_code               1566930
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C25(H25A,H25B), C49(H49A,H49B), C38(H38A,H38B), C46(H46A,H46B)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C11(H11), C19(H19), C21(H21), C23(H23), C27(H27), C39(H39),
 C41(H41), C43(H43), C47(H47), C6(H6), C8(H8), C20(H20), C24(H24), C30(H30),
 C34(H34), C36(H36), C40(H40), C44(H44), C48(H48), C50(H50)
2.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C45(H45A,H45B,H45C), C51(H51A,H51B,H51C), C53(H53A,H53B,
 H53C), C26(H26A,H26B,H26C), C32(H32A,H32B,H32C), C52(H52A,H52B,H52C), C54(H54A,
 H54B,H54C)
;
_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 4.231
_oxdiff_exptl_absorpt_empirical_full_min 0.295