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_4517849
_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         'C17 H19 N3 O Pd, H2 O, C2 H3 N'
_chemical_formula_sum            'C19 H24 N4 O2 Pd'
_chemical_formula_weight         446.82
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-29
_audit_creation_method
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Olex2 1.2
(compiled 2018.05.18 svn.r3508 for OlexSys, GUI svn.r5497)
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_cell_angle_alpha                90
_cell_angle_beta                 92.295(7)
_cell_angle_gamma                90
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_cell_length_a                   14.1106(10)
_cell_length_b                   6.7889(5)
_cell_length_c                   20.7976(17)
_cell_measurement_reflns_used    1985
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      29.4233
_cell_measurement_theta_min      2.9945
_cell_volume                     1990.7(3)
_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)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293.15
_diffrn_detector_area_resol_mean 10.3592
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
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  1 omega  -50.00   30.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.4683   93.0000  -56.0000 80

  2 omega  -87.00   19.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.4683  -77.0000 -180.0000 106
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_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0475277000
_diffrn_orient_matrix_UB_12      -0.0081856000
_diffrn_orient_matrix_UB_13      0.0121297000
_diffrn_orient_matrix_UB_21      0.0162176000
_diffrn_orient_matrix_UB_22      0.0398862000
_diffrn_orient_matrix_UB_23      -0.0291162000
_diffrn_orient_matrix_UB_31      -0.0026826000
_diffrn_orient_matrix_UB_32      0.0962004000
_diffrn_orient_matrix_UB_33      0.0130891000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0407
_diffrn_reflns_av_unetI/netI     0.0596
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -13
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_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            8006
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.349
_diffrn_reflns_theta_min         3.157
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.952
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_exptl_absorpt_correction_T_min  0.85732
_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    1.491
_exptl_crystal_description       plate
_exptl_crystal_F_000             912
_exptl_crystal_size_max          0.43
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.366
_refine_diff_density_min         -0.665
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     245
_refine_ls_number_reflns         3625
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0572
_refine_ls_R_factor_gt           0.0383
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0331P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0777
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_reflns_Friedel_coverage         0.000
_reflns_number_gt                2826
_reflns_number_total             3625
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c02025_si_002.cif
_cod_data_source_block           180529_ly_6_41
_cod_depositor_comments
'Adding full bibliography for 4517848--4517849.cif.'
_cod_database_code               4517849
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'c h n o pd'
_shelx_estimated_absorpt_t_max   0.894
_shelx_estimated_absorpt_t_min   0.685
_reflns_odcompleteness_completeness 99.59
_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, All N(H) groups, All O(H) groups
2. Restrained distances
 O2-H2B
 0.85 with sigma of 0.02
3.a Free rotating group:
 O2(H2A)
3.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C13(H13A,H13B)
3.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C7(H7), C8(H8), C9(H9)
3.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C19(H19A,H19B,
 H19C)
;
_shelx_res_checksum              25923
_shelx_hkl_checksum              66767
_olex2_submission_special_instructions 'No special instructions were received'