Study of Intermediates in Iridium-(Phosphoramidite,Olefin)-Catalyzed Enantioselective Allylic Substitution.
Rössler, Simon L; Krautwald, Simon; Carreira, Erick M.; Journal of the American Chemical Society 139 (2017) 3603–3606; doi:10.1021/jacs.6b12421

data_4131222
_publ_section_title
;
 Study of Intermediates in Iridium-(Phosphoramidite,Olefin)-Catalyzed
 Enantioselective Allylic Substitution.
;
_journal_issue                   10
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3603
_journal_page_last               3606
_journal_paper_doi               10.1021/jacs.6b12421
_journal_volume                  139
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C34 H22 N O2 P'
_chemical_formula_sum            'C34 H22 N O2 P'
_chemical_formula_weight         507.49
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2016-11-11
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.07 svn.r3352 for OlexSys, GUI svn.r5261)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.0300(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.02330(10)
_cell_length_b                   7.58550(10)
_cell_length_c                   13.99810(10)
_cell_measurement_reflns_used    30093
_cell_measurement_temperature    173.2(1)
_cell_measurement_theta_max      78.6060
_cell_measurement_theta_min      3.1970
_cell_volume                     1269.60(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.9f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.9f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.9f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.2(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 300K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -73.00  15.00   0.50    0.15    --  -50.21  77.00 -90.00  176
  2  \w   -125.00 -40.00   0.50    0.15    --  -50.21 -38.00 150.00  170
  3  \w   -115.00 -28.00   0.50    0.15    --  -50.21 -77.00  90.00  174
  4  \w     59.00 120.00   0.50    0.15    --   50.21 178.00  90.00  122
  5  \w    -95.00  -9.00   0.50    0.40    --  -70.00 125.00  90.00  172
  6  \w    -85.00   1.00   0.50    0.40    --  -70.00  57.00   0.00  172
  7  \w   -145.00 -60.00   0.50    0.40    --  -70.00 -38.00-150.00  170
  8  \w     39.00 111.00   0.50    0.40    --  107.75 -99.00   0.00  144
  9  \w     33.00  70.00   0.50    0.40    --  107.75 -38.00-180.00   74
 10  \w     39.00 111.00   0.50    0.40    --  107.75 -99.00  60.00  144
 11  \w     33.00  70.00   0.50    0.40    --  107.75 -38.00 150.00   74
 12  \w     33.00  70.00   0.50    0.40    --  107.75 -38.00   0.00   74
 13  \w     39.00 111.00   0.50    0.40    --  107.75 -99.00 -90.00  144
 14  \w     33.00  70.00   0.50    0.40    --  107.75 -38.00  60.00   74
 15  \w     33.00  76.00   0.50    0.40    --  107.75 -19.00  90.00   86
 16  \w     43.00 130.00   0.50    0.40    --  107.75 -77.00 120.00  174
 17  \w     33.00  70.00   0.50    0.40    --  107.75 -38.00  30.00   74
 18  \w     33.00  70.00   0.50    0.40    --  107.75 -38.00 -30.00   74
 19  \w     97.00 178.00   0.50    0.40    --  107.75  19.00 -30.00  162
 20  \w     37.00 106.00   0.50    0.40    --  107.75 -57.00-120.00  138
 21  \w     39.00 111.00   0.50    0.40    --  107.75 -99.00-180.00  144
 22  \w     37.00 106.00   0.50    0.40    --  107.75 -57.00  90.00  138
 23  \w     33.00  76.00   0.50    0.40    --  107.75 -19.00  30.00   86
 24  \w     39.00 111.00   0.50    0.40    --  107.75 -99.00  90.00  144
 25  \w     33.00  70.00   0.50    0.40    --  107.75 -38.00 -60.00   74
 26  \w     97.00 178.00   0.50    0.40    --  107.75  19.00-150.00  162
 27  \w     38.00 121.00   0.50    0.40    --  107.75-125.00   0.00  166
 28  \w     33.00  76.00   0.50    0.40    --  107.75 -19.00-150.00   86
 29  \w     98.00 178.00   0.50    0.40    --  107.75  38.00  30.00  160
 30  \w   -115.00 -28.00   0.50    0.15    --  -50.21 -77.00  30.00  174
 31  \w   -115.00 -28.00   0.50    0.15    --  -50.21 -77.00 -60.00  174
 32  \w   -121.00 -35.00   0.50    0.15    --  -50.21 -57.00 -60.00  172
 33  \w   -115.00 -28.00   0.50    0.15    --  -50.21 -77.00 150.00  174
 34  \w   -135.00 -87.00   0.50    0.40    --  -70.00 -77.00-150.00   96
 35  \w   -135.00 -47.00   0.50    0.40    --  -70.00 -77.00 -60.00  176
 36  \w   -135.00 -47.00   0.50    0.40    --  -70.00 -77.00  60.00  176
 37  \w   -135.00 -47.00   0.50    0.40    --  -70.00 -77.00 120.00  176
 38  \w   -135.00 -47.00   0.50    0.40    --  -70.00 -77.00   0.00  176
 39  \w   -135.00 -47.00   0.50    0.40    --  -70.00 -77.00-120.00  176
 40  \w   -135.00 -47.00   0.50    0.40    --  -70.00 -77.00-180.00  176
 41  \w   -135.00 -47.00   0.50    0.40    --  -70.00 -77.00 -90.00  176
 42  \w     85.00 173.00   0.50    0.40    --  107.75  77.00 -30.00  176
 43  \w     93.00 178.00   0.50    0.40    --  107.75  57.00 150.00  170
 44  \w     97.00 178.00   0.50    0.40    --  107.75  19.00-120.00  162
 45  \w     85.00 173.00   0.50    0.40    --  107.75  77.00  60.00  176
 46  \w     98.00 178.00   0.50    0.40    --  107.75  38.00 120.00  160
 47  \w     85.00 173.00   0.50    0.40    --  107.75  77.00  30.00  176
 48  \w     85.00 173.00   0.50    0.40    --  107.75  77.00 -90.00  176
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 300K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0980021000
_diffrn_orient_matrix_UB_12      -0.0185813000
_diffrn_orient_matrix_UB_13      0.0795913000
_diffrn_orient_matrix_UB_21      0.0827758000
_diffrn_orient_matrix_UB_22      0.0503041000
_diffrn_orient_matrix_UB_23      -0.0723403000
_diffrn_orient_matrix_UB_31      -0.0120899000
_diffrn_orient_matrix_UB_32      0.1958561000
_diffrn_orient_matrix_UB_33      0.0261034000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0311
_diffrn_reflns_av_unetI/netI     0.0166
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            33861
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.071
_diffrn_reflns_theta_max         67.071
_diffrn_reflns_theta_min         3.175
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.218
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78785
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.9f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.328
_exptl_crystal_description       block
_exptl_crystal_F_000             528
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.162
_refine_diff_density_min         -0.174
_refine_diff_density_rms         0.028
_refine_ls_abs_structure_details
;
 Flack x determined using 1898 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.003(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     470
_refine_ls_number_reflns         4392
_refine_ls_number_restraints     382
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0236
_refine_ls_R_factor_gt           0.0233
_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^)+(0.0438P)^2^+0.0878P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0627
_refine_ls_wR_factor_ref         0.0630
_reflns_Friedel_coverage         0.800
_reflns_Friedel_fraction_full    0.945
_reflns_Friedel_fraction_max     0.945
_reflns_number_gt                4334
_reflns_number_total             4392
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b12421_si_002.cif
_cod_data_source_block           ca101116_1_1
_cod_database_code               4131222
_chemical_oxdiff_formula         'C11 H10 N O'
_chemical_oxdiff_usercomment     'C6 H4 N2 O'
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 N1-C20A \\sim N1-C20 \\sim N1-C22 \\sim N1-C22A
 with sigma of 0.02
 C26A-C20A \\sim C26-C20 \\sim C28A-C22A \\sim C28-C22
 with sigma of 0.02
 C24A-C20A \\sim C24-C20 \\sim C27-C22 \\sim C27A-C22A
 with sigma of 0.02
 C31-C24 \\sim C31A-C24A \\sim C34-C27 \\sim C34A-C27A
 with sigma of 0.02
 C34-C30 \\sim C34A-C30A \\sim C31A-C29A \\sim C31-C29
 with sigma of 0.02
 C33A-C29A \\sim C33-C29 \\sim C30-C25 \\sim C30A-C25A
 with sigma of 0.02
 C33A-C26A \\sim C33-C26 \\sim C28A-C25A \\sim C28-C25
 with sigma of 0.02
 C26-C23 \\sim C26A-C23A \\sim C32A-C28A \\sim C32-C28
 with sigma of 0.02
 C32A-C23A \\sim C32-C23
 with sigma of 0.02
3. Restrained planarity
 C28A, C25A, C30A, C34A, C27A, C22A
 with sigma of 0.1
 C31A, C29A, C33A, C26A, C20A, C24A
 with sigma of 0.1
 C22, C25, C27, C28, C30, C34
 with sigma of 0.1
 C20, C24, C26, C29, C31, C33
 with sigma of 0.1
4. Rigid bond restraints
 N1, C20, C22, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32, C33, C34,
 C31A, C29A, C33A, C26A, C20A, C24A, C23A, C32A, C28A, C25A, C30A, C34A, C27A,
 C22A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Rigid body (RIGU) restrains
 N1, C20, C22, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32, C33, C34,
 C31A, C29A, C33A, C26A, C20A, C24A, C23A, C32A, C28A, C25A, C30A, C34A, C27A,
 C22A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C20A)=Sof(C22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24A)=Sof(C25A)=
 Sof(H25A)=Sof(C26A)=Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(C29A)=Sof(H29A)=
 Sof(C30A)=Sof(H30A)=Sof(C31A)=Sof(H31A)=Sof(C32A)=Sof(H32A)=Sof(C33A)=
 Sof(H33A)=Sof(C34A)=Sof(H34A)=1-FVAR(1)
 Sof(C20)=Sof(C22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24)=Sof(C25)=Sof(H25)=
 Sof(C26)=Sof(C27)=Sof(H27)=Sof(C28)=Sof(C29)=Sof(H29)=Sof(C30)=Sof(H30)=
 Sof(C31)=Sof(H31)=Sof(C32)=Sof(H32)=Sof(C33)=Sof(H33)=Sof(C34)=Sof(H34)=FVAR(1)
7.a Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C15(H15), C16(H16),
 C17(H17), C18(H18), C19(H19), C21(H21), C23(H23), C24(H24), C25(H25), C27(H27),
  C29(H29), C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C23A(H23A),
 C24A(H24A), C25A(H25A), C27A(H27A), C29A(H29A), C30A(H30A), C31A(H31A),
 C32A(H32A), C33A(H33A), C34A(H34A)
;
_shelx_res_checksum              15577
_shelx_hkl_checksum              10409
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-11-10
_olex2_date_sample_submission    2016-11-10
_olex2_submission_original_sample_id ca101116_1_1
_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 1.277
_oxdiff_exptl_absorpt_empirical_full_min 0.831