Mechanistic Investigation of the Nickel-Catalyzed Suzuki Reaction of N,O-Acetals: Evidence for Boronic Acid Assisted Oxidative Addition and an Iminium Activation Pathway
Kevin T. Sylvester; Kevin Wu; Abigail G. Doyle; Journal of the American Chemical Society 134 (2012) 16967–16970; doi:10.1021/ja3079362

data_4118771
_publ_section_title
;
 Mechanistic Investigation of the Nickel-Catalyzed Suzuki Reaction of
 N,O-Acetals: Evidence for Boronic Acid Assisted Oxidative Addition and an
 Iminium Activation Pathway
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              16967
_journal_page_last               16970
_journal_paper_doi               10.1021/ja3079362
_journal_volume                  134
_journal_year                    2012
_chemical_formula_sum            'C79 H61 B F15 N Ni O5 P2'
_chemical_formula_weight         1520.75
_chemical_name_systematic
;
 ?
;
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                103.497(3)
_cell_angle_beta                 100.949(3)
_cell_angle_gamma                115.919(2)
_cell_formula_units_Z            2
_cell_length_a                   14.2780(5)
_cell_length_b                   16.2816(6)
_cell_length_c                   17.9728(10)
_cell_measurement_reflns_used    9975
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      65.98
_cell_measurement_theta_min      3.23
_cell_volume                     3444.5(3)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'ORTEP3 (Farraguia, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SIR92 (Giacavazzo, 1993)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 'ACTA 50'
_diffrn_measured_fraction_theta_max 0.929
_diffrn_measurement_device_type  'Bruker APEX II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0282
_diffrn_reflns_av_sigmaI/netI    0.0287
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            29624
_diffrn_reflns_theta_full        'ACTA 50'
_diffrn_reflns_theta_max         66.20
_diffrn_reflns_theta_min         2.68
_exptl_absorpt_coefficient_mu    1.676
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.6725
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS V2008/1 (Bruker AXS)'
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.466
_exptl_crystal_description       parallelipid
_exptl_crystal_F_000             1560
_exptl_crystal_size_max          0.098
_exptl_crystal_size_mid          0.068
_exptl_crystal_size_min          0.035
_refine_diff_density_max         1.130
_refine_diff_density_min         -0.891
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     892
_refine_ls_number_reflns         11205
_refine_ls_number_restraints     66
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0651
_refine_ls_R_factor_gt           0.0557
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0941P)^2^+5.2115P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1574
_refine_ls_wR_factor_ref         0.1677
_reflns_number_gt                9538
_reflns_number_total             11205
_reflns_threshold_expression     >2\s(I)
_cod_data_source_file            ja3079362_si_003.cif
_cod_data_source_block           kts2
_cod_original_cell_volume        3444.4(3)
_cod_database_code               4118771