Remote γ-C(sp3)‒H Alkylation of Aliphatic Carboxamides via an Unexpected Regiodetermining Pd Migration Process: Reaction Development and Mechanistic Study
Li, Ya; Zhang, Pan; Liu, Yue-Jin; Yu, Zhi-Xiang; Shi, Bing-Feng; ACS Catalysis  (2020) 8212–8222; doi:10.1021/acscatal.0c02025

data_4517848
_publ_section_title
;
 Remote \g-C(sp3)--H Alkylation of Aliphatic Carboxamides via an
 Unexpected Regiodetermining Pd Migration Process: Reaction Development
 and Mechanistic Study
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              8212
_journal_page_last               8222
_journal_paper_doi               10.1021/acscatal.0c02025
_journal_year                    2020
_chemical_formula_moiety         'C25 H24 N2 O2 Pd'
_chemical_formula_sum            'C25 H24 N2 O2 Pd'
_chemical_formula_weight         490.86
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-08-14
_audit_creation_method
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Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
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_cell_angle_alpha                103.496(5)
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_cell_formula_units_Z            2
_cell_length_a                   9.3968(5)
_cell_length_b                   9.4840(5)
_cell_length_c                   11.9025(6)
_cell_measurement_reflns_used    3581
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      29.2577
_cell_measurement_theta_min      1.7608
_cell_volume                     1028.55(10)
_computing_cell_refinement
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CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
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_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
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_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
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_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
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_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      296.15
_diffrn_detector_area_resol_mean 10.3592
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
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  1 omega  -35.00   54.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.3121   77.0000    0.0000 89

  2 omega   -2.00   90.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       11.6246   77.0000  -90.0000 92

  3 omega  -16.00   76.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       11.6246   77.0000  150.0000 92
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_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
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_diffrn_orient_matrix_UB_12      -0.0170218000
_diffrn_orient_matrix_UB_13      -0.0045897000
_diffrn_orient_matrix_UB_21      -0.0027957000
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_diffrn_orient_matrix_UB_31      0.0146159000
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_diffrn_orient_matrix_UB_33      -0.0113600000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0464
_diffrn_reflns_av_unetI/netI     0.0715
_diffrn_reflns_Laue_measured_fraction_full 0.996
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_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -11
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_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            6866
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.347
_diffrn_reflns_theta_min         2.173
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.927
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_exptl_absorpt_correction_T_min  0.81943
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.585
_exptl_crystal_description       needle
_exptl_crystal_F_000             500
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.497
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_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     273
_refine_ls_number_reflns         3750
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0556
_refine_ls_R_factor_gt           0.0407
_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^)+(0.0150P)^2^+0.1460P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
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_reflns_Friedel_coverage         0.000
_reflns_number_gt                3166
_reflns_number_total             3750
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c02025_si_003.cif
_cod_data_source_block           180813_ly_6_intd_2nd
_cod_depositor_comments
'Adding full bibliography for 4517848--4517849.cif.'
_cod_database_code               4517848
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'c h n o pd'
_shelx_estimated_absorpt_t_max   0.851
_shelx_estimated_absorpt_t_min   0.731
_reflns_odcompleteness_completeness 99.60
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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 Ternary CH refined with riding coordinates:
 C13(H13), C14(H14), C16(H16), C17(H17)
2.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C15(H15A,H15B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C7(H7), C8(H8), C9(H9), C20(H20), C21(H21), C22(H22),
 C23(H23)
2.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              22278
_shelx_hkl_checksum              22615
_olex2_submission_special_instructions 'No special instructions were received'