Ir-Catalyzed Intermolecular Branch-Selective Allylic C-H Amidation of Unactivated Terminal Olefins.
Lei, Honghui; Rovis, Tomislav; Journal of the American Chemical Society 141 (2019) 2268–2273; doi:10.1021/jacs.9b00237

data_4128209
_publ_section_title
;
 Ir-Catalyzed Intermolecular Branch-Selective Allylic C-H Amidation of
 Unactivated Terminal Olefins.
;
_journal_issue                   6
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              2268
_journal_page_last               2273
_journal_paper_doi               10.1021/jacs.9b00237
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C27 H42 Ir N O2 S'
_chemical_formula_sum            'C27 H42 Ir N O2 S'
_chemical_formula_weight         636.87
_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
_audit_creation_date             2018-08-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.383(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.3025(5)
_cell_length_b                   8.4734(2)
_cell_length_c                   20.1181(7)
_cell_measurement_reflns_used    4906
_cell_measurement_temperature    200.00(10)
_cell_measurement_theta_max      26.9670
_cell_measurement_theta_min      3.7880
_cell_volume                     2724.40(14)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      200(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0549
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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      0.00  83.00   1.00    8.00    --   17.19  57.00 150.00   83
  2  \w    -37.00 -11.00   1.00    8.00    --  -14.69  77.00   0.00   26
  3  \w    -15.00  14.00   1.00    8.00    --  -14.69 -19.00-120.00   29
  4  \w     31.00  57.00   1.00    8.00    --   17.19  57.00-150.00   26
  5  \w    -52.00  36.00   1.00    8.00    --   17.19 -37.00   0.00   88
  6  \w     47.00  74.00   1.00    8.00    --   17.19-131.00  10.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0368830000
_diffrn_orient_matrix_UB_12      -0.0097233000
_diffrn_orient_matrix_UB_13      -0.0251070000
_diffrn_orient_matrix_UB_21      0.0239148000
_diffrn_orient_matrix_UB_22      0.0064298000
_diffrn_orient_matrix_UB_23      -0.0257327000
_diffrn_orient_matrix_UB_31      0.0062025000
_diffrn_orient_matrix_UB_32      -0.0828869000
_diffrn_orient_matrix_UB_33      0.0009450000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0428
_diffrn_reflns_av_unetI/netI     0.0585
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            14976
_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         26.372
_diffrn_reflns_theta_min         3.505
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    5.000
_exptl_absorpt_correction_T_max  0.915
_exptl_absorpt_correction_T_min  0.653
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
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    1.553
_exptl_crystal_description       prism
_exptl_crystal_F_000             1280
_exptl_crystal_size_max          0.165
_exptl_crystal_size_mid          0.083
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.745
_refine_diff_density_min         -0.554
_refine_diff_density_rms         0.122
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     315
_refine_ls_number_reflns         5559
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0491
_refine_ls_R_factor_gt           0.0341
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0167P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0552
_refine_ls_wR_factor_ref         0.0616
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4435
_reflns_number_total             5559
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b00237_si_002.cif
_cod_data_source_block           honghui2b
_cod_database_code               4128209
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C27 H42 Ir N O2 S'
_reflns_odcompleteness_completeness 99.67
_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 Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B)
2.b Aromatic/amide H refined with riding coordinates:
 C16(H16), C17(H17), C19(H19), C20(H20)
2.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C21(H21A,H21B,H21C), C36(H36A,H36B,H36C), C37(H37A,H37B,
 H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C)
;
_shelx_res_checksum              5296
_shelx_hkl_checksum              58177
_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 1.096
_oxdiff_exptl_absorpt_empirical_full_min 0.910