Mechanistic Study of Asymmetric Oxidative Biaryl Coupling: Evidence for Self-Processing of the Copper Catalyst to Achieve Control of Oxidase vs Oxygenase Activity
J. Brian Hewgley; Shannon S. Stahl; Marisa C. Kozlowski; Journal of the American Chemical Society 130 (2008) 12232–12233; doi:10.1021/ja804570b

data_4108353
_publ_section_title
;
 Mechanistic Study of Asymmetric Oxidative Biaryl Coupling: Evidence for
 Self-Processing of the Copper Catalyst to Achieve Control of Oxidase vs
 Oxygenase Activity
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              12232
_journal_page_last               12233
_journal_paper_doi               10.1021/ja804570b
_journal_volume                  130
_journal_year                    2008
_chemical_absolute_configuration rmad
_chemical_formula_sum            'C8 H16 Cu I N2'
_chemical_formula_weight         330.67
_space_group_IT_number           20
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      20
_symmetry_space_group_name_Hall  'C 2c 2'
_symmetry_space_group_name_H-M   'C 2 2 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_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                   8.9975(15)
_cell_length_b                   12.9799(19)
_cell_length_c                   9.8043(16)
_cell_measurement_temperature    143(1)
_cell_volume                     1145.0(3)
_computing_data_collection       'CrystalClear (Rigaku, 1999)'
_computing_data_reduction        'CrystalClear (Rigaku, 1999)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SIR97 (Altomare, 1999)'
_diffrn_ambient_temperature      143(1)
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device       'CCD Area Detector'
_diffrn_measurement_device_type  'Rigaku Mercury'
_diffrn_measurement_method       'phi and omega rotations'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'rotating anode'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0270
_diffrn_reflns_av_sigmaI/netI    0.0258
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            3284
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         25.00
_diffrn_reflns_theta_min         2.75
_exptl_absorpt_coefficient_mu    4.559
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7013
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;  Shape and scale corrections using equivalent reflections.
    Shape function based on spherical harmonics.
    Highest even and odd order for spherical harmonics:  4  and  3
    Laue group:  mmm
    Friedel opposites are equivalent.
;
_exptl_crystal_density_diffrn    1.918
_exptl_crystal_F_000             640
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.438
_refine_diff_density_min         -0.980
_refine_diff_density_rms         0.107
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.03(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     57
_refine_ls_number_reflns         995
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.098
_refine_ls_R_factor_all          0.0331
_refine_ls_R_factor_gt           0.0296
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0476P)^2^+0.2870P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0765
_refine_ls_wR_factor_ref         0.0786
_reflns_number_gt                911
_reflns_number_total             995
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja804570b_si_002.cif
_cod_data_source_block           shelxl
_cod_original_sg_symbol_H-M      'C 2 2 21 '
_cod_database_code               4108353