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_4131218
_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, 0.58(C4 H10 O), 2.84(C H Cl3)'
_chemical_formula_sum            'C82.15 H62.62 Cl9.53 Ir N2 O5.58 P2'
_chemical_formula_weight         1759.17
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-07-19
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.739(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.1166(6)
_cell_length_b                   22.3594(11)
_cell_length_c                   15.6267(9)
_cell_measurement_reflns_used    9842
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      30.21
_cell_measurement_theta_min      4.17
_cell_volume                     3882.4(4)
_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 0.989
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker/Nonius Kappa Apex2'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'double mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0280
_diffrn_reflns_av_unetI/netI     0.0740
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            35250
_diffrn_reflns_point_group_measured_fraction_full 0.940
_diffrn_reflns_point_group_measured_fraction_max 0.930
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_min         5.099
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms high brilliance'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.142
_exptl_absorpt_correction_T_max  0.6928
_exptl_absorpt_correction_T_min  0.6249
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1076 before and 0.0693 after correction.
The Ratio of minimum to maximum transmission is 0.9020.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear light brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.505
_exptl_crystal_description       plate
_exptl_crystal_F_000             1766
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.04
_refine_diff_density_max         2.206
_refine_diff_density_min         -0.864
_refine_diff_density_rms         0.108
_refine_ls_abs_structure_details
;
 Flack x determined using 6387 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.006(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1039
_refine_ls_number_reflns         16589
_refine_ls_number_restraints     319
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0389
_refine_ls_R_factor_gt           0.0351
_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^)+(0.0333P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0881
_refine_ls_wR_factor_ref         0.0897
_reflns_Friedel_coverage         0.829
_reflns_Friedel_fraction_full    0.888
_reflns_Friedel_fraction_max     0.866
_reflns_number_gt                15307
_reflns_number_total             16589
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b12421_si_002.cif
_cod_data_source_block           ca050216_1_1_0m
_cod_database_code               4131218
_shelx_estimated_absorpt_t_max   0.919
_shelx_estimated_absorpt_t_min   0.699
_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
 O51-C56 = O51-C54
 1.41 with sigma of 0.002
 O50-C52 = O50-C50
 1.41 with sigma of 0.002
 C52-C53 = C51-C50
 1.51 with sigma of 0.002
 C56-C57 = C55-C54
 1.51 with sigma of 0.002
 C28B-H28B = C27B-H27B
 0.95 with sigma of 0.01
 C5-C4 \\sim C5-C6 \\sim C6-C7 \\sim C7-C8 \\sim C8-C9 \\sim C9-C4
 with sigma of 0.02
 Cl57-C60 \\sim Cl58-C60 \\sim Cl56-C60 \\sim Cl51_$1-C58_$1 \\sim
Cl50_$1-C58_$1 \\sim Cl52_$1-
 C58_$1
 with sigma of 0.02
 O51-C56 \\sim O51-C54 \\sim O50-C52 \\sim O50-C50
 with sigma of 0.02
 C56-C57 \\sim C55-C54 \\sim C52-C53 \\sim C51-C50
 with sigma of 0.02
3. Rigid bond restraints
 O50, C50, C51, C52, C53, O51, C54, C55, C56, C57, Cl50, Cl51, Cl52, C58, Cl53,
  Cl54, Cl55, C59, Cl56, Cl57, Cl58, C60, Cl59, Cl60, Cl61, C61
 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(C53) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(O50) \\sim Ueq, Uanis(C50)
\\sim Ueq, Uanis(C51) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(C57) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(O51) \\sim Ueq, Uanis(C54)
\\sim Ueq, Uanis(C55) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(Cl50) \\sim Ueq, Uanis(Cl52) \\sim Ueq, Uanis(Cl51) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C4, C5, C6, C7, C8, C9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O50, C50, C51, C52, C53, O51, C54, C55, C56, C57, Cl50, Cl51, Cl52, C58, Cl53,
  Cl54, Cl55, C59, Cl56, Cl57, Cl58, C60, Cl59, Cl60, Cl61, C61
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(O51)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=
 Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=0.66666*(1-
 FVAR(2))
 Sof(O50)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=
 Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=0.33333*(1-
 FVAR(2))
 Sof(Cl50)=Sof(Cl51)=Sof(Cl52)=Sof(C58)=Sof(H58)=Sof(Cl56)=Sof(Cl57)=Sof(Cl58)=
 Sof(C60)=Sof(H60)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C58(H58), C59(H59), C60(H60), C61(H61)
7.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C50(H50A,H50B), C52(H52A,H52B), C54(H54A,H54B), C56(H56A,H56B)
7.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C2A(H2A), C3A(H3A), C5A(H5A),
 C6A(H6A), C7A(H7A), C8A(H8A), C13A(H13A), C14A(H14A), C15A(H15A), C16A(H16A),
 C18A(H18A), C19A(H19A), C22A(H22A), C23A(H23A), C24A(H24A), C25A(H25A),
 C27A(H27A), C28A(H28A), C30A(H30A), C31A(H31A), C32A(H32A), C33A(H33A),
 C2B(H2B), C3B(H3B), C5B(H5B), C6B(H6B), C7B(H7B), C8B(H8B), C13B(H13B),
 C14B(H14B), C15B(H15B), C16B(H16B), C18B(H18B), C19B(H19B), C22B(H22B),
 C23B(H23B), C24B(H24B), C25B(H25B), C30B(H30B), C31B(H31B), C32B(H32B),
 C33B(H33B)
7.d Idealised Me refined as rotating group:
 C51(H51A,H51B,H51C), C53(H53A,H53B,H53C), C55(H55A,H55B,H55C), C57(H57A,H57B,
 H57C)
7.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              91869
_shelx_hkl_checksum              76428
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-02-05
_olex2_date_sample_submission    2016-02-05
_olex2_submission_original_sample_id ca050216_1_1
_olex2_submission_special_instructions 'No special instructions were received'