Palladium(II)-Catalyzed Stereospecific Alkenyl C‒H Bond Alkylation of Allylamines with Alkyl Iodides
Luo, Yun-Cheng; Yang, Chao; Qiu, Sheng-Qi; Liang, Qiu-Ju; Xu, Yun-He; Loh, Teck-Peng; ACS Catalysis 9 (2019) 4271–; doi:10.1021/acscatal.8b04415

data_4514706
_publ_section_title
;
 Palladium(II)-Catalyzed Stereospecific Alkenyl C--H Bond Alkylation of
 Allylamines with Alkyl Iodides
;
_journal_issue                   5
_journal_name_full               'ACS Catalysis'
_journal_page_first              4271
_journal_paper_doi               10.1021/acscatal.8b04415
_journal_volume                  9
_journal_year                    2019
_chemical_formula_moiety         'C28 H26 N4 O2 Pd'
_chemical_formula_sum            'C28 H26 N4 O2 Pd'
_chemical_formula_weight         556.93
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-09-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.460(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.3908(2)
_cell_length_b                   20.0893(6)
_cell_length_c                   14.6398(4)
_cell_measurement_reflns_used    4592
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.3070
_cell_measurement_theta_min      3.7500
_cell_volume                     2426.75(12)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.974
_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    -66.00  28.00   1.00    2.00    --  -40.98  38.00  60.00   94
  2  \w     46.00  80.00   1.00    2.00    --   40.98 -99.00-150.00   34
  3  \w     85.00 112.00   1.00    5.00    --  106.95 -61.00 -30.00   27
  4  \w     68.00 107.00   1.00    5.00    --  106.95 -95.00   0.00   39
  5  \w     53.00  80.00   1.00    2.00    --   40.98-133.00 116.00   27
  6  \w     25.00  55.00   1.00    5.00    --  106.95 -95.00   0.00   30
  7  \w     44.00  77.00   1.00    5.00    --  106.95 -61.00 -30.00   33
  8  \w     25.00  68.00   1.00    5.00    --  106.95 -95.00 -90.00   43
  9  \w     52.00 107.00   1.00    5.00    --  106.95 -95.00-180.00   55
 10  \w     79.00 155.00   1.00    5.00    --  106.95  61.00-150.00   76
 11  \w    153.00 178.00   1.00    5.00    --  106.95  77.00 -60.00   25
 12  \w    105.00 132.00   1.00    5.00    --  106.95  77.00 -60.00   27
 13  \w     79.00 178.00   1.00    5.00    --  106.95  61.00  90.00   99
 14  \w   -111.00 -16.00   1.00    2.00    --  -40.98 -38.00-120.00   95
 15  \w   -113.00 -88.00   1.00    2.00    --  -41.23-136.00 -61.00   25
 16  \w    -34.00  48.00   1.00    2.00    --   41.23 -77.00 150.00   82
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0388067000
_diffrn_orient_matrix_UB_12      -0.0665775000
_diffrn_orient_matrix_UB_13      0.0514072000
_diffrn_orient_matrix_UB_21      0.0645953000
_diffrn_orient_matrix_UB_22      0.0379955000
_diffrn_orient_matrix_UB_23      0.0906084000
_diffrn_orient_matrix_UB_31      -0.1708074000
_diffrn_orient_matrix_UB_32      -0.0007313000
_diffrn_orient_matrix_UB_33      0.0246708000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0733
_diffrn_reflns_av_unetI/netI     0.0821
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            10871
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.431
_diffrn_reflns_theta_min         3.777
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.434
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.41278
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.524
_exptl_crystal_description       block
_exptl_crystal_F_000             1136
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.432
_refine_diff_density_min         -1.470
_refine_diff_density_rms         0.167
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     334
_refine_ls_number_reflns         4757
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0861
_refine_ls_R_factor_gt           0.0703
_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^)+(0.0225P)^2^+51.0695P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1842
_refine_ls_wR_factor_ref         0.1918
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3949
_reflns_number_total             4757
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b04415_si_002.cif
_cod_data_source_block           657--d-p_2
_cod_original_cell_volume        2426.77(11)
_cod_database_code               4514706
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.98
_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. Uiso/Uaniso restraints and constraints
Uanis(C1) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C2) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
3.a Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C11(H11A,H11B)
3.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C21(H21), C4(H4), C20(H20), C9(H9), C6(H6), C16(H16), C8(H8),
 C18(H18), C5(H5), C15(H15), C19(H19)
3.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C28(H28A,H28B,H28C)
;
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.768
_oxdiff_exptl_absorpt_empirical_full_min 0.163