The Allyl Intermediate in Regioselective and Enantioselective Iridium-Catalyzed Asymmetric Allylic Substitution Reactions
Sherzod T. Madrahimov; Dean Markovic; John F. Hartwig; Journal of the American Chemical Society 131 (2009) 7228–7229; doi:10.1021/ja902609g

data_4104455
_publ_contact_author
; 
Scott R. Wilson 
University of Illinois 
School of Chemical Sciences, Box 59-1 
505 South Mathews Avenue 
Urbana, Illinois  61801 
USA 
;
_publ_contact_author_email       srwilson@uiuc.edu
_publ_contact_author_fax         '1  217 244 8068'
_publ_contact_author_phone       '1  217 244 1708'
_publ_section_title
;
 The Allyl Intermediate in Regioselective and Enantioselective
 Iridium-Catalyzed Asymmetric Allylic Substitution Reactions
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7228
_journal_page_last               7229
_journal_paper_doi               10.1021/ja902609g
_journal_volume                  131
_journal_year                    2009
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C47 H46 Ir N O2 P, 2(C6 H6), C F3 O3 S'
_chemical_formula_sum            'C60 H58 F3 Ir N O5 P S'
_chemical_formula_weight         1185.30
_chemical_name_systematic
; 
? 
;
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_audit_update_record
; 
2008-01-06   text and data added, srw 
;
_cell_angle_alpha                90.00
_cell_angle_beta                 115.6920(10)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   11.4816(7)
_cell_length_b                   20.3721(13)
_cell_length_c                   12.4196(8)
_cell_measurement_reflns_used    8958
_cell_measurement_temperature    193(2)
_cell_measurement_theta_max      29.79
_cell_measurement_theta_min      2.21
_cell_volume                     2617.8(3)
_computing_cell_refinement       'SAINT V7.23A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2.0-1 (Bruker, 2004)'
_computing_data_reduction
; 
SAINT V7.23A, XPREP V2005/2, SADABS V2007/4 (Bruker, 2005 & 2007) 
;
_computing_molecular_graphics    'SHELXTL V6.12 (Bruker, 2005)'
_computing_publication_material  'XCIF V6.12 (Bruker, 2005)'
_computing_structure_refinement  'SHELXTL V6.12 (Bruker, 2005)'
_computing_structure_solution    'SHELXTL V6.12 (Bruker, 2005)'
_diffrn_ambient_temperature      193(2)
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_device       'Bruker Kappa/ApexII CCD'
_diffrn_measurement_method       'profile data from \f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_wavelength_id  ga49xas
_diffrn_reflns_av_R_equivalents  0.0244
_diffrn_reflns_av_sigmaI/netI    0.0268
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            14424
_diffrn_reflns_theta_full        29.82
_diffrn_reflns_theta_max         29.82
_diffrn_reflns_theta_min         1.82
_exptl_absorpt_coefficient_mu    2.682
_exptl_absorpt_correction_T_max  0.6291
_exptl_absorpt_correction_T_min  0.4553
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details   'SHELXTL/XPREP V2005/2 (Bruker, 2005)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.504
_exptl_crystal_description       prism
_exptl_crystal_F_000             1200
_exptl_crystal_id                ga49xas
_exptl_crystal_preparation
; 
The data crystal was mounted using oil (Parantone-N, Exxon) to a 
0.3 mm cryo-loop (Hampton Research) with the (3 -2 -4) scattering 
planes roughly normal to the spindle axis. 
;
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.43
_exptl_crystal_size_min          0.24
_refine_diff_density_max         1.382
_refine_diff_density_min         -0.479
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details 'Flack (1983, 2000),  6862 Friedels'
_refine_ls_abs_structure_Flack   -0.020(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     684
_refine_ls_number_reflns         14424
_refine_ls_number_restraints     97
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0224
_refine_ls_R_factor_gt           0.0197
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0252P)^2^+0.3438P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0468
_refine_ls_wR_factor_ref         0.0479
_reflns_number_gt                13720
_reflns_number_total             14424
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja902609g_si_002.cif
_cod_data_source_block           compound2a
_cod_original_sg_symbol_Hall     'P 2yb '
_cod_original_sg_symbol_H-M      'P 21 '
_cod_database_code               4104455