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_1566931
_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_formula_moiety         'C30 H29 N O2'
_chemical_formula_sum            'C30 H30 N O2'
_chemical_formula_weight         436.55
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2020-09-09
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2021-11-25 deposited with the CCDC.	2022-05-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.679(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.2005(6)
_cell_length_b                   19.9331(9)
_cell_length_c                   9.2145(3)
_cell_measurement_reflns_used    2943
_cell_measurement_temperature    293.16(10)
_cell_measurement_theta_max      69.4780
_cell_measurement_theta_min      8.0460
_cell_volume                     2416.50(17)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      293.16(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    150.00 176.00   1.00    1.00    --  108.00  63.00  30.00   26
  2  \w     81.00 178.00   1.00    1.00    --  108.00  25.00 -30.00   97
  3  \w     80.00 170.00   1.00    1.00    --  108.00  25.00-120.00   90
  4  \w     78.00 113.00   1.00    1.00    --  108.00-111.00-120.00   35
  5  \w     47.00 122.00   1.00    1.00    --  108.00 -50.00 -60.00   75
  6  \w     48.00 110.00   1.00    1.00    --   54.00  57.00 -30.00   62
  7  \w     44.00 108.00   1.00    1.00    --   54.00  57.00-150.00   64
  8  \w     38.00 108.00   1.00    1.00    --  108.00 -50.00-120.00   70
  9  \w     38.00 138.00   1.00    1.00    --  108.00 -91.00 -90.00  100
 10  \w     40.00 115.00   1.00    1.00    --   54.00  57.00  90.00   75
 11  \w     30.00  55.00   1.00    1.00    --   54.00 -57.00 -60.00   25
 12  \w     31.00  90.00   1.00    1.00    --   54.00-125.00 -60.00   59
 13  \w     -4.00  21.00   1.00    1.00    --    0.00 -57.00-150.00   25
 14  \w     24.00  62.00   1.00    1.00    --    0.00  57.00-180.00   38
 15  \w     19.00  44.00   1.00    1.00    --    0.00  57.00 -30.00   25
 16  \w    -66.00 -41.00   1.00    1.00    --    0.00 -57.00-150.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0853069000
_diffrn_orient_matrix_UB_12      0.0019205000
_diffrn_orient_matrix_UB_13      -0.1044506000
_diffrn_orient_matrix_UB_21      -0.0801312000
_diffrn_orient_matrix_UB_22      0.0024314000
_diffrn_orient_matrix_UB_23      -0.1311744000
_diffrn_orient_matrix_UB_31      0.0003606000
_diffrn_orient_matrix_UB_32      0.0772317000
_diffrn_orient_matrix_UB_33      0.0066265000
_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  0.0270
_diffrn_reflns_av_unetI/netI     0.0314
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            8748
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        66.592
_diffrn_reflns_theta_max         66.592
_diffrn_reflns_theta_min         4.026
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.579
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45977
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
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    1.200
_exptl_crystal_description       block
_exptl_crystal_F_000             932
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.421
_refine_diff_density_min         -0.472
_refine_diff_density_rms         0.109
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     301
_refine_ls_number_reflns         4260
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0906
_refine_ls_R_factor_gt           0.0779
_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^)+(0.1206P)^2^+0.6502P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1936
_refine_ls_wR_factor_ref         0.2125
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3367
_reflns_number_total             4260
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc01887j2.cif
_cod_data_source_block           weiwx_0907
_cod_original_cell_volume        2416.51(18)
_cod_database_code               1566931
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.96
_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:
 C9(H9A,H9B), C13(H13A,H13B), C32(H32A,H32B)
2.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22),
 C25(H25), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30), C31(H31)
2.c Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C0AA(H0AA,H0AB,H0AC)
;
_shelx_res_checksum              15074
_shelx_hkl_checksum              14954
_olex2_date_sample_data_collection 2020-09-07
_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 2.017
_oxdiff_exptl_absorpt_empirical_full_min 0.447