Identification of an Activated Catalyst in the Iridium-Catalyzed Allylic Amination and Etherification. Increased Rates, Scope, and Selectivity
Christoph A. Kiener; Chutian Shu; Christopher Incarvito; John F. Hartwig; Journal of the American Chemical Society 125 (2003) 14272–14273; doi:10.1021/ja038319h

data_4114414
_publ_section_title
;
 Identification of an Activated Catalyst in the Iridium-Catalyzed Allylic
 Amination and Etherification. Increased Rates, Scope, and Selectivity
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14272
_journal_page_last               14273
_journal_paper_doi               10.1021/ja038319h
_journal_volume                  125
_journal_year                    2003
_chemical_absolute_configuration ad
_chemical_formula_sum            'C47 H50 Ir N O2 P2'
_chemical_formula_weight         915.02
_chemical_name_systematic
;
  ?
;
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   10.150(2)
_cell_length_b                   19.125(4)
_cell_length_c                   20.818(4)
_cell_measurement_temperature    173(2)
_cell_volume                     4041.2(14)
_computing_cell_refinement       Denzo
_computing_data_collection       'Nonius Collect'
_computing_data_reduction        Denzo
_computing_molecular_graphics    XP
_computing_publication_material  XCIF
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      173(2)
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Nonius KappaCCD'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0000
_diffrn_reflns_av_sigmaI/netI    0.0645
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            9647
_diffrn_reflns_theta_full        28.27
_diffrn_reflns_theta_max         28.27
_diffrn_reflns_theta_min         2.23
_exptl_absorpt_coefficient_mu    3.422
_exptl_absorpt_correction_T_max  0.5477
_exptl_absorpt_correction_T_min  0.4266
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.504
_exptl_crystal_description       block
_exptl_crystal_F_000             1848
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.20
_refine_diff_density_max         0.588
_refine_diff_density_min         -1.057
_refine_diff_density_rms         0.113
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.001(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.003
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     478
_refine_ls_number_reflns         9647
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.003
_refine_ls_R_factor_all          0.0542
_refine_ls_R_factor_gt           0.0371
_refine_ls_shift/su_max          0.032
_refine_ls_shift/su_mean         0.003
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0349P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0685
_refine_ls_wR_factor_ref         0.0740
_reflns_number_gt                8156
_reflns_number_total             9647
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja038319h_2.cif
_cod_data_source_block           ckien02
_cod_original_cell_volume        4041.3(14)
_cod_database_code               4114414