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_4131219
_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_formula_moiety
'C77 H52 Cl Ir N3 O6 P2, 5(C H Cl3), C F3 O3 S'
_chemical_formula_sum            'C83 H57 Cl16 F3 Ir N3 O9 P2 S'
_chemical_formula_weight         2150.71
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-07-08
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                91.892(3)
_cell_angle_beta                 108.143(3)
_cell_angle_gamma                115.526(2)
_cell_formula_units_Z            2
_cell_length_a                   15.7403(19)
_cell_length_b                   17.473(2)
_cell_length_c                   18.238(2)
_cell_measurement_reflns_used    9981
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      30.03
_cell_measurement_theta_min      2.45
_cell_volume                     4218.8(9)
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0436
_diffrn_reflns_av_unetI/netI     0.0597
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            65541
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.508
_diffrn_reflns_theta_min         2.499
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.218
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6624
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0673 before and 0.0468 after correction.
The Ratio of minimum to maximum transmission is 0.8878.
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    1.693
_exptl_crystal_description       plate
_exptl_crystal_F_000             2140
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.03
_refine_diff_density_max         2.023
_refine_diff_density_min         -1.218
_refine_diff_density_rms         0.137
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1227
_refine_ls_number_reflns         25681
_refine_ls_number_restraints     315
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0514
_refine_ls_R_factor_gt           0.0397
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0441P)^2^+2.4310P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0886
_refine_ls_wR_factor_ref         0.0945
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21863
_reflns_number_total             25681
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b12421_si_002.cif
_cod_data_source_block           ca150316_1_1_0m
_cod_original_cell_volume        4219.0(9)
_cod_database_code               4131219
_shelx_estimated_absorpt_t_max   0.936
_shelx_estimated_absorpt_t_min   0.718
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 Cl71-C55 \\sim Cl56-C54 \\sim Cl73-C55 \\sim Cl57-C54 \\sim Cl58-C54 \\sim
Cl72-C55
 with sigma of 0.02
 Cl62-C2AA \\sim Cl78-C2AA \\sim Cl77-C2AA \\sim Cl63-C2AA \\sim Cl64-C2AA
\\sim Cl79-C2AA
 with sigma of 0.02
 Cl74-C1D \\sim Cl59-C1D \\sim Cl61-C1D \\sim Cl76-C1D \\sim Cl60-C1D \\sim
Cl75-C1D
 with sigma of 0.02
 Cl65-C53 \\sim Cl66-C53 \\sim Cl54-C52 \\sim Cl55-C52 \\sim Cl67-C53 \\sim
Cl53-C52
 with sigma of 0.02
 Cl69-C50 \\sim Cl52-C51 \\sim Cl70-C50 \\sim Cl51-C51 \\sim Cl68-C50 \\sim
Cl50-C51
 with sigma of 0.02
3. Rigid bond restraints
 Cl56, Cl57, Cl58, C54, Cl71, Cl72, Cl73, C55
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C2AA, Cl62, Cl63, Cl64, Cl77, Cl78, Cl79
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1D, Cl59, Cl60, Cl61, Cl74, Cl75, Cl76
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl53, Cl54, Cl55, C52, Cl65, Cl66, Cl67, C53
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl50, Cl51, Cl52, C51, Cl68, Cl69, Cl70, C50
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Rigid body (RIGU) restrains
 Cl56, Cl57, Cl58, C54, Cl71, Cl72, Cl73, C55
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C2AA, Cl62, Cl63, Cl64, Cl77, Cl78, Cl79
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1D, Cl59, Cl60, Cl61, Cl74, Cl75, Cl76
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl53, Cl54, Cl55, C52, Cl65, Cl66, Cl67, C53
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl50, Cl51, Cl52, C51, Cl68, Cl69, Cl70, C50
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Cl65)=Sof(Cl66)=Sof(Cl67)=Sof(C53)=Sof(H53)=Sof(H1DA)=Sof(Cl74)=Sof(Cl75)=
 Sof(Cl76)=Sof(H2AB)=Sof(Cl77)=Sof(Cl78)=Sof(Cl79)=Sof(Cl68)=Sof(Cl69)=
 Sof(Cl70)=Sof(C50)=Sof(H50)=1-FVAR(1)
 Sof(Cl53)=Sof(Cl54)=Sof(Cl55)=Sof(C52)=Sof(H52)=Sof(H1D)=Sof(Cl59)=Sof(Cl60)=
 Sof(Cl61)=Sof(H2AA)=Sof(Cl62)=Sof(Cl63)=Sof(Cl64)=Sof(Cl50)=Sof(Cl51)=
 Sof(Cl52)=Sof(C51)=Sof(H51)=FVAR(1)
 Sof(Cl71)=Sof(Cl72)=Sof(Cl73)=Sof(C55)=Sof(H55)=1-FVAR(2)
 Sof(Cl56)=Sof(Cl57)=Sof(Cl58)=Sof(C54)=Sof(H54)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C27B(H27B), C28B(H28B), C52(H52), C53(H53), C54(H54),
 C55(H55), C1D(H1D), C1D(H1DA), C2AA(H2AA), C2AA(H2AB), C51(H51), C50(H50)
6.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B)
6.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), 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)
;
_shelx_res_checksum              12688
_shelx_hkl_checksum              1716
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-03-15
_olex2_date_sample_submission    2016-03-14
_olex2_submission_original_sample_id ca150316_1_1
_olex2_submission_special_instructions 'No special instructions were received'