Mechanistic Studies of a Palladium-Catalyzed Intramolecular Hydroamination of Unactivated Alkenes: Protonolysis of a Stable Palladium Alkyl Complex Is the Turnover-Limiting Step
Brian M. Cochran; Forrest E. Michael; Journal of the American Chemical Society 130 (2008) 2786–2792; doi:10.1021/ja0734997

data_4107478
_publ_contact_author_address
;
Department of Chemistry, BOX 351700
University of Washington
Seattle, WA 98195
USA
;
_publ_contact_author_email       wernerka@u.washington.edu
_publ_contact_author_name        'Werner Kaminsky'
_publ_section_title
;
 Mechanistic Studies of a Palladium-Catalyzed Intramolecular
 Hydroamination of Unactivated Alkenes: Protonolysis of a Stable Palladium
 Alkyl Complex Is the Turnover-Limiting Step
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              2786
_journal_page_last               2792
_journal_paper_doi               10.1021/ja0734997
_journal_volume                  130
_journal_year                    2008
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C40 H43 N2 O P2 Pd, C5 H12, B F4'
_chemical_formula_sum            'C45 H55 B F4 N2 O P2 Pd'
_chemical_formula_weight         895.06
_chemical_name_common            bmc-f-43-1
_chemical_name_systematic        bmc-f-43-1
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      19
_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                   10.4480(3)
_cell_length_b                   12.8160(4)
_cell_length_c                   32.8480(11)
_cell_measurement_reflns_used    126
_cell_measurement_temperature    130(2)
_cell_volume                     4398.4(2)
_computing_cell_refinement       'HKL Scalepack (Otwinowski & Minor 1997)'
_computing_data_collection       KappaCCD
_computing_data_reduction        'HKL Scalepack (Otwinowski & Minor 1997)'
_computing_molecular_graphics    'maXus, Zortep'
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    SIR97
_diffrn_ambient_temperature      130(2)
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Nonius KappaCCD'
_diffrn_measurement_method       '\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_reflns_av_R_equivalents  0.1560
_diffrn_reflns_av_sigmaI/netI    0.2460
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            8786
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         26.37
_diffrn_reflns_theta_min         2.05
_exptl_absorpt_coefficient_mu    0.547
_exptl_absorpt_correction_T_max  0.9732
_exptl_absorpt_correction_T_min  0.8799
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   HKL2000
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.352
_exptl_crystal_description       'cut block'
_exptl_crystal_F_000             1856
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.020
_refine_diff_density_min         -1.042
_refine_diff_density_rms         0.115
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.43(5)
_refine_ls_extinction_coef       0.0014(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   0.996
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     511
_refine_ls_number_reflns         8786
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      0.997
_refine_ls_R_factor_all          0.2049
_refine_ls_R_factor_gt           0.0693
_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^)+(0.0409P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1164
_refine_ls_wR_factor_ref         0.1501
_reflns_number_gt                3676
_reflns_number_total             8786
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            ja0734997-file003.cif
_cod_data_source_block           shelxl
_cod_database_code               4107478