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_4131221
_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
'3(C68 H44 Cl Ir N2 O6 P2), 12(C H Cl3), 2(C4 H10 O)'
_chemical_formula_sum            'C224 H164 Cl39 Ir3 N6 O20 P6'
_chemical_formula_weight         5404.57
_space_group_crystal_system      trigonal
_space_group_IT_number           145
_space_group_name_Hall           'P 32'
_space_group_name_H-M_alt        'P 32'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-11-10
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   32.9074(6)
_cell_length_b                   32.9074(6)
_cell_length_c                   17.7716(4)
_cell_measurement_reflns_used    9943
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      66.49
_cell_measurement_theta_min      2.69
_cell_volume                     16666.5(6)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.961
_diffrn_measured_fraction_theta_max 0.961
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker Kappa Apex2 Duo'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'focusing graphite'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0695
_diffrn_reflns_av_unetI/netI     0.0610
_diffrn_reflns_Laue_measured_fraction_full 0.940
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -38
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            134768
_diffrn_reflns_point_group_measured_fraction_full 0.658
_diffrn_reflns_point_group_measured_fraction_max 0.659
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         66.728
_diffrn_reflns_theta_min         2.685
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    8.662
_exptl_absorpt_correction_T_max  0.7420
_exptl_absorpt_correction_T_min  0.5214
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0975 before and 0.0786 after correction.
The Ratio of minimum to maximum transmission is 0.7027.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.615
_exptl_crystal_description       block
_exptl_crystal_F_000             8082
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.04
_refine_diff_density_max         3.070
_refine_diff_density_min         -2.155
_refine_diff_density_rms         0.144
_refine_ls_abs_structure_details
;
 Flack x determined using 6026 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.005(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.202
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2853
_refine_ls_number_reflns         25920
_refine_ls_number_restraints     3756
_refine_ls_restrained_S_all      1.180
_refine_ls_R_factor_all          0.0620
_refine_ls_R_factor_gt           0.0579
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1523
_refine_ls_wR_factor_ref         0.1558
_reflns_Friedel_coverage         0.371
_reflns_Friedel_fraction_full    0.349
_reflns_Friedel_fraction_max     0.356
_reflns_number_gt                24161
_reflns_number_total             25920
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b12421_si_002.cif
_cod_data_source_block           cu_ca011015_4_1_0m
_cod_original_cell_volume        16666.5(7)
_cod_database_code               4131221
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.723
_shelx_estimated_absorpt_t_min   0.377
_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
 O203-C202
 1.55 with sigma of 0.02
 C204-O203
 1.55 with sigma of 0.02
 C202-C201 = C201-H20I = C205-C204
 1.477 with sigma of 0.02
 Cl31-Cl33
 2.897 with sigma of 0.02
 Cl32-Cl33
 2.897 with sigma of 0.02
 Cl32-Cl31
 2.897 with sigma of 0.02
 Cl31-C10D = Cl33-C10D = Cl32-C10D
 1.742 with sigma of 0.02
 Cl2E-Cl1E
 2.897 with sigma of 0.02
 Cl1E-C10E = Cl3E-C10E = Cl2E-C10E
 1.742 with sigma of 0.02
 Cl1E-Cl3E
 2.897 with sigma of 0.02
 Cl2E-Cl3E
 2.897 with sigma of 0.02
 Cl26-Cl25
 2.897 with sigma of 0.02
 Cl27-Cl25
 2.897 with sigma of 0.02
 Cl27-Cl26
 2.897 with sigma of 0.02
 Cl5E-Cl26
 2.897 with sigma of 0.02
 Cl4E-Cl26
 2.897 with sigma of 0.02
 Cl5E-Cl4E
 2.897 with sigma of 0.02
 Cl26-C8D = Cl27-C8D = Cl25-C8D
 1.742 with sigma of 0.02
 Cl26-C8E = Cl4E-C8E = Cl5E-C8E
 1.742 with sigma of 0.02
 Cl9E-Cl7E
 2.897 with sigma of 0.02
 Cl30-Cl29
 2.897 with sigma of 0.02
 Cl28-Cl29
 2.897 with sigma of 0.02
 Cl28-Cl30
 2.897 with sigma of 0.02
 Cl30-C9D = Cl28-C9D = Cl29-C9D
 1.742 with sigma of 0.02
 Cl8E-Cl9E
 2.897 with sigma of 0.02
 Cl7E-Cl8E
 2.897 with sigma of 0.02
 Cl7E-C9E = Cl9E-C9E = Cl8E-C9E
 1.742 with sigma of 0.02
 Cl22-Cl23
 2.897 with sigma of 0.02
 Cl2F-Cl1F
 2.897 with sigma of 0.02
 Cl24-Cl22
 2.897 with sigma of 0.02
 Cl23-Cl24
 2.897 with sigma of 0.02
 Cl3F-Cl2F
 2.897 with sigma of 0.02
 Cl3F-Cl1F
 2.897 with sigma of 0.02
 Cl22-C11D = Cl23-C11D = Cl24-C11D
 1.742 with sigma of 0.02
 Cl35-C12D = Cl36-C12D = Cl34-C12D
 1.742 with sigma of 0.02
 Cl35-Cl36
 2.897 with sigma of 0.02
 Cl36-Cl34
 2.897 with sigma of 0.02
 Cl34-Cl35
 2.897 with sigma of 0.02
 Cl6F-Cl5F
 2.897 with sigma of 0.02
 Cl5F-Cl4F
 2.897 with sigma of 0.02
 Cl6F-Cl4F
 2.897 with sigma of 0.02
 Cl5F-C12E = Cl6F-C12E = Cl4F-C12E
 1.742 with sigma of 0.02
 Cl1F-C11E = Cl3F-C11E = Cl2F-C11E
 1.742 with sigma of 0.02
 O102-C101 \\sim O102-C103
 with sigma of 0.02
 C104-C103 \\sim C101-C100
 with sigma of 0.02
 C202-C201 \\sim C205-C204
 with sigma of 0.02
 O203-C204 \\sim O203-C202
 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C201) \\sim Ueq, Uanis(C202) \\sim Ueq, Uanis(O203) \\sim Ueq,
Uanis(C204) \\sim Ueq, Uanis(C205) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(Cl27) \\sim Ueq, Uanis(Cl25) \\sim Ueq, Uanis(C8D) \\sim Ueq, Uanis(Cl4E)
\\sim Ueq, Uanis(C8E) \\sim Ueq, Uanis(Cl5E) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uanis(Cl9E) \\sim Ueq, Uanis(Cl8E) \\sim Ueq, Uanis(Cl7E) \\sim Ueq, Uanis(C9E)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(Cl36) \\sim Ueq, Uanis(Cl4F) \\sim Ueq, Uanis(Cl35) \\sim Ueq,
Uanis(C12D) \\sim Ueq, Uanis(Cl34) \\sim Ueq, Uanis(Cl6F) \\sim Ueq,
Uanis(Cl5F) \\sim Ueq, Uanis(C12E) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C10D) = Uanis(C10E)
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(Cl1E)=Sof(Cl2E)=Sof(C10E)=Sof(H10N)=Sof(Cl3E)=Sof(C8E)=Sof(H8E)=Sof(Cl4E)=
 Sof(Cl5E)=Sof(Cl8E)=Sof(C9E)=Sof(H9E)=Sof(Cl9E)=Sof(Cl7E)=Sof(Cl3F)=Sof(Cl1F)=
 Sof(C11E)=Sof(H11E)=Sof(Cl2F)=Sof(Cl35)=Sof(Cl36)=Sof(Cl34)=Sof(C12D)=
 Sof(H12D)=1-FVAR(1)
 Sof(Cl25)=Sof(Cl27)=Sof(Cl22)=Sof(Cl23)=Sof(Cl24)=Sof(C11D)=Sof(H11D)=
 Sof(C8D)=Sof(H8D)=Sof(Cl33)=Sof(Cl30)=Sof(Cl28)=Sof(Cl29)=Sof(C9D)=Sof(H9D)=
 Sof(Cl32)=Sof(C10D)=Sof(H10M)=Sof(Cl31)=Sof(Cl4F)=Sof(Cl6F)=Sof(C12E)=
 Sof(H12E)=Sof(Cl5F)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C2C(H2C), C1C(H1C), C2A(H2A), C1B(H1B), C4D(H4D), C1A(H1A), C2B(H2B),
 C2D(H2D), C6D(H6D), C5D(H5D), C3D(H3D), C1D(H1D), C7D(H7D), C11D(H11D),
 C8D(H8D), C9D(H9D), C10D(H10M), C10E(H10N), C8E(H8E), C9E(H9E), C11E(H11E),
 C12D(H12D), C12E(H12E)
7.b Secondary CH2 refined with riding coordinates:
 C103(H10A,H10D), C101(H10H,H10I), C202(H20A,H20B), C204(H20F,H20G)
7.c Aromatic/amide H refined with riding coordinates:
 C17C(H17C), C25A(H25A), C16C(H16C), C7C(H7C), C27C(H27C), C18C(H18C),
 C16B(H16B), C26C(H26C), C24C(H24C), C13C(H13C), C28A(H28A), C33C(H33C),
 C66C(H66C), C47C(H47C), C67C(H67C), C17B(H17B), C19C(H19C), C25C(H25C),
 C51A(H51A), C22B(H22B), C46B(H46B), C46C(H46C), C6C(H6C), C36C(H36C),
 C34A(H34A), C35A(H35A), C56C(H56C), C21A(H21A), C21C(H21C), C51B(H51B),
 C18B(H18B), C22C(H22C), C50A(H50A), C21B(H21B), C36A(H36A), C66A(H66A),
 C5C(H5C), C10C(H10C), C26A(H26A), C47B(H47B), C54B(H54B), C31A(H31A),
 C23A(H23A), C10B(H10B), C53C(H53C), C12C(H12C), C53B(H53B), C42C(H42C),
 C67B(H67B), C56B(H56B), C4C(H4C), C5A(H5A), C50C(H50C), C51C(H51C), C61B(H61B),
  C55B(H55B), C41C(H41C), C66B(H66B), C7A(H7A), C44B(H44B), C24A(H24A),
 C19B(H19B), C61A(H61A), C4B(H4B), C33A(H33A), C6B(H6B), C55A(H55A), C30C(H30C),
  C31C(H31C), C54A(H54A), C62B(H62B), C12A(H12A), C5B(H5B), C41A(H41A),
 C34C(H34C), C55C(H55C), C53A(H53A), C44A(H44A), C62A(H62A), C42B(H42B),
 C47A(H47A), C7B(H7B), C11A(H11A), C13B(H13B), C63A(H63A), C41B(H41B),
 C43B(H43B), C64A(H64A), C64B(H64B), C4A(H4A), C11B(H11B), C42A(H42A),
 C43A(H43A), C46A(H46A), C63B(H63B), C67A(H67A), C50B(H50B), C27B(H27B),
 C26B(H26B), C25B(H25B), C28B(H28B), C35C(H35C), C30B(H30B), C16A(H16A),
 C33B(H33B), C43C(H43C), C19A(H19A), C54C(H54C), C18A(H18A), C11C(H11C),
 C36B(H36B), C44C(H44C), C17A(H17A), C35B(H35B), C30A(H30A), C31B(H31B),
 C62C(H62C), C61C(H61C), C63C(H63C), C14A(H14A), C64C(H64C), C58A(H58A),
 C12B(H12B), C34B(H34B), C13A(H13A), C6A(H6A)
7.d Idealised Me refined as rotating group:
 C100(H10E,H10F,H10G), C104(H10J,H10K,H10L), C205(H20C,H20D,H20E), C201(H20H,
 H20I,H20J)
;
_shelx_res_checksum              38247
_shelx_hkl_checksum              72351
_olex2_date_sample_data_collection 2015-11-06
_olex2_date_sample_submission    2015-11-05
_olex2_exptl_crystal_mounting_method
'Crystal mounted in high viscosity perfluoropolyalkyl ether oil and slowly cooled to 100K. Otherwise fast decomposition (2h).'
_olex2_submission_original_sample_id ca011015_4_1
_olex2_submission_special_instructions 'No special instructions were received'