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_4131217
_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
'C77 H54 Cl Ir N2 O5 P2, 1.74(C4 H10 O), 1.26(C H Cl3)'
_chemical_formula_sum            'C85.24 H72.7 Cl4.76 Ir N2 O6.74 P2'
_chemical_formula_weight         1655.95
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2015-09-14
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.8812(8)
_cell_length_b                   19.5634(10)
_cell_length_c                   22.8793(12)
_cell_measurement_reflns_used    9865
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      30.48
_cell_measurement_theta_min      2.43
_cell_volume                     7108.4(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    'XT (Sheldrick, 2015)'
_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 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker Apex2 Duo (Mo)'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'focusing graphite'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0661
_diffrn_reflns_av_unetI/netI     0.0406
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            163499
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.545
_diffrn_reflns_theta_min         1.561
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.163
_exptl_absorpt_correction_T_max  0.3325
_exptl_absorpt_correction_T_min  0.2586
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0710 before and 0.0608 after correction.
The Ratio of minimum to maximum transmission is 0.7777.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.547
_exptl_crystal_description       block
_exptl_crystal_F_000             3360
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.773
_refine_diff_density_min         -1.131
_refine_diff_density_rms         0.086
_refine_ls_abs_structure_details
;
 Flack x determined using 9163 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.0055(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     967
_refine_ls_number_reflns         21732
_refine_ls_number_restraints     67
_refine_ls_restrained_S_all      2.085
_refine_ls_R_factor_all          0.0292
_refine_ls_R_factor_gt           0.0270
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0242P)^2^+2.7104P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0589
_refine_ls_wR_factor_ref         0.0596
_reflns_Friedel_coverage         0.850
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                20823
_reflns_number_total             21732
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b12421_si_002.cif
_cod_data_source_block           mo_ca020915_1_1_0m
_cod_original_formula_sum        'C85.24 H72.70 Cl4.76 Ir N2 O6.74 P2'
_cod_database_code               4131217
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.846
_shelx_estimated_absorpt_t_min   0.544
_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, All O(H) groups
2. Restrained distances
 Cl30-Cl30
 2.885 with sigma of 0.02
 Cl30-Cl30
 2.885 with sigma of 0.02
 Cl30-Cl30
 2.885 with sigma of 0.02
 Cl30-C304 = Cl3-C304 = Cl2-C304
 1.75 with sigma of 0.02
 C1-H1A = C1-H1B
 0.99 with sigma of 0.001
 H1A-H1B
 1.654 with sigma of 0.001
 O300-C301 \\sim O300-C302
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(Cl30) \\sim Ueq, Uanis(Cl2) \\sim Ueq, Uanis(Cl3) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 O300, C300, C301, C302, C303, Cl2, Cl3, Cl30, C304
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Cl2)=Sof(Cl3)=Sof(Cl30)=Sof(C304)=Sof(H304)=1-FVAR(1)
 Sof(O300)=Sof(C300)=Sof(H30C)=Sof(H30D)=Sof(H30E)=Sof(C301)=Sof(H30F)=
 Sof(H30G)=Sof(C302)=Sof(H30H)=Sof(H30I)=Sof(C303)=Sof(H30J)=Sof(H30K)=
 Sof(H30L)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C27B(H27B), C28B(H28B), C304(H304), C100(H100)
6.b Secondary CH2 refined with riding coordinates:
 C301(H30F,H30G), C302(H30H,H30I), C201(H20D,H20E), C202(H20F,H20G)
6.c Aromatic/amide H refined with riding coordinates:
 C2A(H2A), C2B(H2B), C3A(H3A), C3B(H3B), C5(H5), C5A(H5A), C5B(H5B), C6(H6),
 C6A(H6A), C6B(H6B), C7(H7), C7A(H7A), C7B(H7B), C8(H8), C8A(H8A), C8B(H8B),
 C9(H9), C13A(H13A), C13B(H13B), C14A(H14A), C14B(H14B), C15A(H15A), C15B(H15B),
  C16A(H16A), C16B(H16B), C18A(H18A), C18B(H18B), C19A(H19A), C19B(H19B),
 C22A(H22A), C22B(H22B), C23A(H23A), C23B(H23B), C24A(H24A), C24B(H24B),
 C25A(H25A), C25B(H25B), C27A(H27A), C28A(H28A), C30A(H30A), C30B(H30B),
 C31A(H31A), C31B(H31B), C32A(H32A), C32B(H32B), C33A(H33A), C33B(H33B)
6.d Idealised Me refined as rotating group:
 C300(H30C,H30D,H30E), C303(H30J,H30K,H30L), C200(H20A,H20B,H20C), C203(H20H,
 H20I,H20J)
6.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              30494
_shelx_hkl_checksum              9900
_olex2_date_sample_data_collection 2015-09-02
_olex2_date_sample_submission    2015-08-28
_olex2_submission_original_sample_id ca020915_1_1
_olex2_submission_special_instructions 'No special instructions were received'