Allylic aminations with hindered secondary amine nucleophiles catalyzed by heterobimetallic Pd-Ti complexes.
Walker, Whitney K.; Anderson, Diana L.; Stokes, Ryjul W.; Smith, Stacey J.; Michaelis, David J.; Organic letters 17 (2015) 752–755; doi:10.1021/acs.orglett.5b00058

data_1554773
_publ_section_title
;
 Allylic aminations with hindered secondary amine nucleophiles catalyzed
 by heterobimetallic Pd-Ti complexes.
;
_journal_issue                   3
_journal_name_full               'Organic letters'
_journal_page_first              752
_journal_page_last               755
_journal_paper_doi               10.1021/acs.orglett.5b00058
_journal_volume                  17
_journal_year                    2015
_chemical_formula_moiety
;
C48 H57 N3 P3 Ti, 0.85[Ti Cl5], 0.15[Ti Cl6 Li], 0.275[C5 H12], 
0.725[C H2 Cl2]
;
_chemical_formula_sum            'C49.05 H59.38 Cl5.87 Li0.15 N3 P3 Ti2'
_chemical_formula_weight         1088.78
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014
_cell_angle_alpha                75.287(3)
_cell_angle_beta                 74.747(3)
_cell_angle_gamma                84.913(3)
_cell_formula_units_Z            2
_cell_length_a                   10.3083(6)
_cell_length_b                   14.3567(7)
_cell_length_c                   19.2355(10)
_cell_measurement_reflns_used    9942
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      69.75
_cell_measurement_theta_min      3.18
_cell_volume                     2655.7(2)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXT (Sheldrick 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0538
_diffrn_reflns_av_unetI/netI     0.0356
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            52696
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.256
_diffrn_reflns_theta_min         3.183
_diffrn_source                   'Bruker-Nonius FR591 Cu rotating anode'
_exptl_absorpt_coefficient_mu    6.404
_exptl_absorpt_correction_T_max  0.3841
_exptl_absorpt_correction_T_min  0.2101
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Sheldrick, 2009)'
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.362
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       flat-needle
_exptl_crystal_F_000             1128
_exptl_crystal_size_max          0.290
_exptl_crystal_size_mid          0.140
_exptl_crystal_size_min          0.080
_refine_diff_density_max         0.671
_refine_diff_density_min         -0.896
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     749
_refine_ls_number_reflns         9931
_refine_ls_number_restraints     1295
_refine_ls_restrained_S_all      1.109
_refine_ls_R_factor_all          0.0484
_refine_ls_R_factor_gt           0.0430
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0518P)^2^+3.5985P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1133
_refine_ls_wR_factor_ref         0.1166
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8937
_reflns_number_total             9931
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b00058_si_002.cif
_cod_data_source_block           14017
_cod_database_code               1554773
_shelx_estimated_absorpt_t_min   0.258
_shelx_estimated_absorpt_t_max   0.628
_shelxl_version_number           2014-3
_shelx_res_checksum              27461
_shelx_hkl_checksum              97075