Palladium-Catalyzed Site-Selective [5 + 1] Annulation of Aromatic Amides with Alkenes: Acceleration of β-Hydride Elimination by Maleic Anhydride from Palladacycle
He, Qiyuan; Yamazaki, Ken; Ano, Yusuke; Chatani, Naoto; ACS Catalysis 12 (2022) 1595–1600; doi:10.1021/acscatal.1c05675

data_4519301
_publ_section_title
;
 Palladium-Catalyzed Site-Selective [5 + 1] Annulation of Aromatic Amides
 with Alkenes: Acceleration of \b-Hydride Elimination by Maleic Anhydride
 from Palladacycle
;
_journal_issue                   2
_journal_name_full               'ACS Catalysis'
_journal_page_first              1595
_journal_page_last               1600
_journal_paper_doi               10.1021/acscatal.1c05675
_journal_volume                  12
_journal_year                    2022
_chemical_formula_moiety         'C20 H19 N O4 S'
_chemical_formula_sum            'C20 H19 N O4 S'
_chemical_formula_weight         369.42
_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     dual
_audit_creation_date             2021-05-13
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.6820(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.4266(2)
_cell_length_b                   7.40710(10)
_cell_length_c                   33.2757(6)
_cell_measurement_reflns_used    10980
_cell_measurement_temperature    123
_cell_measurement_theta_max      67.7280
_cell_measurement_theta_min      3.8210
_cell_volume                     3531.66(9)
_computing_cell_refinement       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      123
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.995
_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    -22.00  33.00   0.50    0.29    --    0.00 -99.00 -60.00  110
  2  \w     28.00  53.00   0.50    0.29    --    0.00-144.00-135.00   50
  3  \w     51.00  76.00   0.50    1.16    --   57.38-144.00-135.00   50
  4  \w     51.00  76.00   0.50    1.16    --   96.50-144.00-135.00   50
  5  \w     18.00  43.00   0.50    0.29    --    0.00-126.00  33.00   50
  6  \w    -58.00 -32.00   0.50    1.16    -- -106.00  63.00-150.00   52
  7  \w    -76.00 -19.00   0.50    1.16    -- -106.00  63.00 -90.00  114
  8  \w    -77.00 -43.00   0.50    1.16    -- -106.00  63.00 -60.00   68
  9  \w    -92.00 -66.00   0.50    1.16    -- -106.00 111.00-120.00   52
 10  \w   -100.00 -74.00   0.50    1.16    -- -106.00 111.00-180.00   52
 11  \w   -101.00 -72.00   0.50    1.16    --  -57.38 144.00 -81.00   58
 12  \w   -125.00 -99.00   0.50    1.16    -- -106.00 144.00 -81.00   52
 13  \w   -110.00 -85.00   0.50    1.16    -- -106.00 111.00 -30.00   50
 14  \w   -103.00 -17.00   0.50    1.16    -- -106.00  99.00   0.70  172
 15  \w    -79.00 -36.00   0.50    1.16    -- -106.00 178.00  60.00   86
 16  \w    -61.00 -20.00   0.50    1.16    -- -106.00 131.00 145.41   82
 17  \w    -66.00 -40.00   0.50    1.16    -- -106.00 130.00 162.42   52
 18  \w    -69.00 -43.00   0.50    1.16    -- -106.00  77.00 150.00   52
 19  \w    -88.00 -63.00   0.50    1.16    --  -57.38 126.00 110.00   50
 20  \w    -66.00 -41.00   0.50    0.29    --    0.00 126.00 110.00   50
 21  \w   -101.00 -37.00   0.50    0.29    --    0.00 178.00 -30.00  128
 22  \w     45.00  70.00   0.50    0.29    --    0.00 178.00  60.00   50
 23  \w     46.00  84.00   0.50    0.29    --    0.00 178.00  90.00   76
 24  \w     83.00 108.00   0.50    1.16    --   57.38 126.00 110.00   50
 25  \w    106.00 132.00   0.50    1.16    --   96.50 126.00 110.00   52
 26  \w    108.00 155.00   0.50    1.16    --   96.50 111.00   0.00   94
 27  \w     77.00 102.00   0.50    1.16    --   57.38 144.00 -81.00   50
 28  \w     40.00  88.00   0.50    0.29    --    0.00 178.00-120.00   96
 29  \w    -92.00 -67.00   0.50    1.16    -- -106.00 126.00 110.00   50
 30  \w    -93.00 -67.00   0.50    1.16    -- -106.00 111.00 150.00   52
 31  \w   -109.00 -17.00   0.50    1.16    -- -106.00  77.00 120.00  184
 32  \w    -96.00 -71.00   0.50    1.16    -- -106.00 -50.00  60.00   50
 33  \w   -131.00-106.00   0.50    1.16    --  -57.38-126.00  33.00   50
 34  \w   -144.00 -80.00   0.50    1.16    --  -57.38 -94.00 120.00  128
 35  \w   -140.00-104.00   0.50    1.16    --  -57.38 -94.00   0.00   72
 36  \w   -139.00 -28.00   0.50    1.16    --  -57.38 -61.00  30.00  222
 37  \w   -121.00 -96.00   0.50    1.16    -- -106.00  63.00-150.00   50
 38  \w   -141.00-115.00   0.50    1.16    -- -106.00  63.00 -60.00   52
 39  \w   -147.00-121.00   0.50    1.16    -- -106.00  50.00   0.00   52
 40  \w   -117.00 -10.00   0.50    1.16    --  -57.38 125.00 150.00  214
 41  \w   -117.00 -92.00   0.50    1.16    -- -106.00 130.00 162.42   50
 42  \w   -121.00 -75.00   0.50    1.16    -- -106.00 131.00 145.41   92
 43  \w   -137.00-111.00   0.50    1.16    -- -106.00  77.00 150.00   52
 44  \w   -152.00-126.00   0.50    1.16    -- -106.00 178.00 120.00   52
 45  \w   -134.00-109.00   0.50    1.16    -- -106.00 178.00  60.00   50
 46  \w   -155.00-130.00   0.50    1.16    -- -106.00 -50.00  60.00   50
 47  \w   -175.00-122.00   0.50    1.16    -- -106.00 -63.00  30.00  106
 48  \w   -132.00-106.00   0.50    1.16    -- -106.00 -91.00 -60.00   52
 49  \w   -149.00 -58.00   0.50    1.16    -- -106.00-144.00-135.00  182
 50  \w   -101.00 -76.00   0.50    1.16    -- -106.00 -91.00-180.00   50
 51  \w   -132.00-106.00   0.50    1.16    -- -106.00 -91.00-180.00   52
 52  \w   -154.00 -81.00   0.50    1.16    --  -57.38 -94.00-180.00  146
 53  \w   -154.00 -72.00   0.50    1.16    -- -106.00 -63.00 -60.00  164
 54  \w   -172.00 -78.00   0.50    1.16    -- -106.00-111.00 -90.00  188
 55  \w   -172.00-146.00   0.50    1.16    -- -106.00 -91.00 -60.00   52
 56  \w   -172.00-141.00   0.50    1.16    -- -106.00-111.00  60.00   62
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0131732000
_diffrn_orient_matrix_UB_12      -0.0660546000
_diffrn_orient_matrix_UB_13      0.0428714000
_diffrn_orient_matrix_UB_21      0.0117465000
_diffrn_orient_matrix_UB_22      -0.1967237000
_diffrn_orient_matrix_UB_23      -0.0135443000
_diffrn_orient_matrix_UB_31      0.1060661000
_diffrn_orient_matrix_UB_32      0.0135649000
_diffrn_orient_matrix_UB_33      0.0123062000
_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  0.0323
_diffrn_reflns_av_unetI/netI     0.0292
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            26810
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.048
_diffrn_reflns_theta_min         3.841
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.851
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93942
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.43a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.390
_exptl_crystal_description       block
_exptl_crystal_F_000             1552
_exptl_crystal_size_max          0.133
_exptl_crystal_size_mid          0.094
_exptl_crystal_size_min          0.063
_refine_diff_density_max         0.578
_refine_diff_density_min         -0.381
_refine_diff_density_rms         0.049
_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     475
_refine_ls_number_reflns         6396
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0434
_refine_ls_R_factor_gt           0.0400
_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^)+(0.0538P)^2^+2.3466P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1062
_refine_ls_wR_factor_ref         0.1090
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5849
_reflns_number_total             6396
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c05675_si_002.cif
_cod_data_source_block           exp_1545
_cod_depositor_comments
;

2025-07-30
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C40 H38 N2 O8 S2'
_cod_original_formula_weight         738.84
_cod_original_formula_moiety         '2(C20 H19 N O4 S)'
_cod_original_formula_units_Z            4
_cod_database_code               4519301
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C20 H19 N1 O4 S1'
_diffrn_oxdiff_ac3_digest_frames
;
01a44a2c8fcb5f7cf3069fce970ee5ec0c00046fa94
;
_diffrn_oxdiff_ac3_digest_hkl
;
01d5da08d1b79043350e9acd95230f9c93a1f4
;
_reflns_odcompleteness_completeness 88.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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:
 C45(H45a,H45b), C19(H19a,H19b)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C29(H29), C38(H38), C15(H15), C41(H41), C6(H6), C8(H8), C12(H12),
 C34(H34), C14(H14), C7(H7), C33(H33), C32(H32), C39(H39), C40(H40), C13(H13)
2.c Idealised Me refined as rotating group:
 C25(H25a,H25b,H25c), C51(H51a,H51b,H51c), C18(H18a,H18b,H18c), C48(H48a,H48b,
 H48c), C22(H22a,H22b,H22c), C44(H44a,H44b,H44c)
;
_shelx_res_checksum              39091
_shelx_hkl_checksum              13644
_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 1.527
_oxdiff_exptl_absorpt_empirical_full_min 0.765