Nickel-Catalyzed Oxidative Coupling of Unactivated C(sp3)–H Bonds in Aliphatic Amides with Terminal Alkynes
Luo, Fei-Xian; Cao, Zhi-Chao; Zhao, Hong-Wei; Wang, Ding; Zhang, Yun-Fei; Xu, Xing; Shi, Zhang-Jie; Organometallics 36 (2017) 18–; doi:10.1021/acs.organomet.6b00529

data_4086891
_publ_section_title
;
 Nickel-Catalyzed Oxidative Coupling of Unactivated C(sp3)--H Bonds in
 Aliphatic Amides with Terminal Alkynes
;
_journal_issue                   1
_journal_name_full               Organometallics
_journal_page_first              18
_journal_paper_doi               10.1021/acs.organomet.6b00529
_journal_volume                  36
_journal_year                    2017
_chemical_formula_moiety         'C31 H37 F3 N2 O Si'
_chemical_formula_sum            'C31 H37 F3 N2 O Si'
_chemical_formula_weight         538.71
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2015-07-06
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                113.800(6)
_cell_angle_beta                 90.996(5)
_cell_angle_gamma                101.075(6)
_cell_formula_units_Z            2
_cell_length_a                   8.4313(6)
_cell_length_b                   12.8023(8)
_cell_length_c                   15.1161(9)
_cell_measurement_reflns_used    3216
_cell_measurement_temperature    180.01(10)
_cell_measurement_theta_max      28.0480
_cell_measurement_theta_min      2.9610
_cell_volume                     1456.87(18)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      180.01(10)
_diffrn_detector_area_resol_mean 10.3914
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.839
_diffrn_measurement_details
;
  1 omega  -39.00   41.00   1.0000    1.0300
omega____ theta____ kappa____ phi______ frames
    -       10.7017  -77.0000   90.0000 80

  2 omega   -1.00   53.00   1.0000    1.0300
omega____ theta____ kappa____ phi______ frames
    -       10.7017  -99.0000    0.0000 54

  3 omega  -65.00   37.00   1.0000    1.0300
omega____ theta____ kappa____ phi______ frames
    -       10.7017  -38.0000  120.0000 102

  4 omega   14.00   87.00   1.0000    1.0300
omega____ theta____ kappa____ phi______ frames
    -       10.7017   38.0000  -90.0000 73

  5 omega  -13.00   29.00   1.0000    1.0300
omega____ theta____ kappa____ phi______ frames
    -      -11.7954  -99.0000  -60.0000 42
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0108855000
_diffrn_orient_matrix_UB_12      0.0486199000
_diffrn_orient_matrix_UB_13      0.0457925000
_diffrn_orient_matrix_UB_21      -0.0766391000
_diffrn_orient_matrix_UB_22      -0.0234305000
_diffrn_orient_matrix_UB_23      0.0108243000
_diffrn_orient_matrix_UB_31      0.0379396000
_diffrn_orient_matrix_UB_32      -0.0305978000
_diffrn_orient_matrix_UB_33      0.0211125000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0362
_diffrn_reflns_av_unetI/netI     0.0645
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.839
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            13233
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.839
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.224
_diffrn_reflns_theta_min         2.857
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.126
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57179
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour
;
;
_exptl_crystal_density_diffrn    1.228
_exptl_crystal_description
;
;
_exptl_crystal_F_000             572
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.360
_refine_diff_density_min         -0.345
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     382
_refine_ls_number_reflns         6640
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.125
_refine_ls_R_factor_all          0.0970
_refine_ls_R_factor_gt           0.0569
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0394P)^2^+0.6165P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1107
_refine_ls_wR_factor_ref         0.1341
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4446
_reflns_number_total             6640
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00529_si_002.cif
_cod_data_source_block           exp_5565
_cod_depositor_comments          'Adding full bibliography for 4086891.cif.'
_cod_original_cell_volume        1456.87(17)
_cod_database_code               4086891
_shelxl_version_number           2014-3
_chemical_oxdiff_formula         'C1 H1 O1 N1 Si1 F1'
_shelx_estimated_absorpt_t_max   0.988
_shelx_estimated_absorpt_t_min   0.981
_reflns_odcompleteness_completeness 99.67
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.97
_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(F3A) \\sim Ueq, Uanis(F3B) \\sim Ueq, Uanis(F2A) \\sim Ueq, Uanis(F1B)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.008
Uanis(F2B) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.005
Uanis(F1A) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.005
3. Others
 Sof(F1B)=Sof(F2B)=Sof(F3B)=1-FVAR(1)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C15(H15), C18(H18), C21(H21)
4.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B)
4.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C6(H6), C7(H7), C8(H8), C26(H26), C27(H27), C28(H28),
 C30(H30)
4.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C)
;
_olex2_submission_special_instructions 'No special instructions were received'