Ligand Controlled Ir-Catalyzed Regiodivergent Oxyamination of Unactivated Alkenes.
Lei, Honghui; Conway, Jr, John H; Cook, Caleb C.; Rovis, Tomislav; Journal of the American Chemical Society 141 (2019) 11864–11869; doi:10.1021/jacs.9b06366

data_4128556
_publ_section_title
;
 Ligand Controlled Ir-Catalyzed Regiodivergent Oxyamination of Unactivated
 Alkenes.
;
_journal_issue                   30
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11864
_journal_page_last               11869
_journal_paper_doi               10.1021/jacs.9b06366
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration unk
_chemical_formula_moiety         '1(C16 H21 N O3)'
_chemical_formula_sum            'C16 H21 N O3'
_chemical_formula_weight         275.34
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'I -2ya'
_space_group_name_H-M_alt        'I 1 a 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2019-06-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 111.129(5)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   22.1740(10)
_cell_length_b                   10.4504(4)
_cell_length_c                   28.6661(14)
_cell_measurement_reflns_used    6662
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      25.9420
_cell_measurement_theta_min      3.8900
_cell_volume                     6196.1(5)
_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)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(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 0.874
_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     14.00  69.00   1.00    5.00    --   17.19  57.00   0.00   55
  2  \w     10.00  65.00   1.00    5.00    --   17.19  77.00  60.00   55
  3  \w     23.00  49.00   1.00    5.00    --  -14.69  37.00 -90.00   26
  4  \w     -5.00  38.00   1.00    5.00    --   17.19  77.00 -30.00   43
  5  \w    -19.00  12.00   1.00    5.00    --   17.19 -99.00   0.00   31
  6  \w     35.00  60.00   1.00    5.00    --   17.19 178.00 120.00   25
  7  \w    -20.00   5.00   1.00    5.00    --   17.19 -99.00-180.00   25
  8  \w     23.00  56.00   1.00    5.00    --   17.19 -99.00-180.00   33
  9  \w     22.00  78.00   1.00    5.00    --   17.19  37.00 150.00   56
 10  \w    -47.00   0.00   1.00    5.00    --   17.19 -57.00-180.00   47
 11  \w      7.00  76.00   1.00    5.00    --   17.19  57.00 -90.00   69
;
_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      -0.0330124000
_diffrn_orient_matrix_UB_12      -0.0019290000
_diffrn_orient_matrix_UB_13      -0.0158684000
_diffrn_orient_matrix_UB_21      -0.0091964000
_diffrn_orient_matrix_UB_22      -0.0027841000
_diffrn_orient_matrix_UB_23      0.0212552000
_diffrn_orient_matrix_UB_31      -0.0013144000
_diffrn_orient_matrix_UB_32      0.0677787000
_diffrn_orient_matrix_UB_33      0.0004258000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0552
_diffrn_reflns_av_unetI/netI     0.0798
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.874
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            30794
_diffrn_reflns_point_group_measured_fraction_full 0.935
_diffrn_reflns_point_group_measured_fraction_max 0.776
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.648
_diffrn_reflns_theta_min         3.407
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.081
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.543
_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    1.181
_exptl_crystal_description       block
_exptl_crystal_F_000             2368
_exptl_crystal_size_max          0.459
_exptl_crystal_size_mid          0.242
_exptl_crystal_size_min          0.121
_refine_diff_density_max         0.407
_refine_diff_density_min         -0.207
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 2847 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -1.3(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     842
_refine_ls_number_reflns         13581
_refine_ls_number_restraints     239
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0963
_refine_ls_R_factor_gt           0.0673
_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^)+(0.0439P)^2^+3.0504P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1246
_refine_ls_wR_factor_ref         0.1432
_reflns_Friedel_coverage         0.774
_reflns_Friedel_fraction_full    0.873
_reflns_Friedel_fraction_max     0.677
_reflns_number_gt                9755
_reflns_number_total             13581
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b06366_si_003.cif
_cod_data_source_block           honghui5
_cod_original_sg_symbol_H-M      'I a'
_cod_database_code               4128556
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C16 H21 O3 N'
_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. Restrained distances
 N1-H1 = N21-H21 = N41-H41 = N61-H61
 0.90175 with sigma of 0.02
3. Restrained planarity
 C7, C8, C9, C10, C11, C12, C13
 with sigma of 0.1
 C7, C8B, C9B, C10B, C11B, C12B, C13B
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1A with sigma of 0.01 and sigma
for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C7, C8, C9, C10, C11, C12, C13, C8B, C9B, C10B, C11B, C12B, C13B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O16, C17, C18, C19, C20, C17B, C18B, C19B, C20B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
{C7, C8B, C9B, C10B, C11B, C12B, C13B} sigma for 1-2: 0.02, 1-3: 0.04
as
{C7, C8, C9, C10, C11, C12, C13}
{O14, C15, O16, C17B, C18B, C19B, C20B} sigma for 1-2: 0.02, 1-3: 0.04
as
{O14, C15, O16, C17, C18, C19, C20}
7. Others
 Sof(C17B)=Sof(C18B)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C19B)=Sof(H19D)=
 Sof(H19E)=Sof(H19F)=Sof(C20B)=Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(1)
 Sof(C17)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19A)=Sof(H19B)=
 Sof(H19C)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=FVAR(1)
 Uiso(H1)=Uiso(H21)=Uiso(H41)=Uiso(H61)=FVAR(3)
 Sof(C8B)=Sof(C9B)=Sof(H9B)=Sof(C10B)=Sof(H10B)=Sof(C11B)=Sof(H11B)=Sof(C12B)=
 Sof(H12B)=Sof(C13B)=Sof(H13B)=1-FVAR(4)
 Sof(C8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)=Sof(C12)=Sof(H12)=
 Sof(C13)=Sof(H13)=FVAR(4)
8.a Ternary CH refined with riding coordinates:
 C6(H6), C7(H7), C26(H26), C27(H27), C46(H46), C47(H47), C66(H66), C67(H67)
8.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B), C24(H24A,H24B), C25(H25A,H25B), C44(H44A,H44B),
 C45(H45A,H45B), C64(H64A,H64B), C65(H65A,H65B)
8.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C9B(H9B), C10B(H10B),
 C11B(H11B), C12B(H12B), C13B(H13B), C29(H29), C30(H30), C31(H31), C32(H32),
 C33(H33), C49(H49), C50(H50), C51(H51), C52(H52), C53(H53), C69(H69), C70(H70),
  C71(H71), C72(H72), C73(H73)
8.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C18B(H18D,H18E,
 H18F), C19B(H19D,H19E,H19F), C20B(H20D,H20E,H20F), C38(H38A,H38B,H38C),
 C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C58(H58A,H58B,H58C), C59(H59A,H59B,
 H59C), C60(H60A,H60B,H60C), C78(H78A,H78B,H78C), C79(H79A,H79B,H79C), C80(H80A,
 H80B,H80C)
;
_shelx_res_checksum              6984
_shelx_hkl_checksum              29130
_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 1.160
_oxdiff_exptl_absorpt_empirical_full_min 0.892