Enantioselective Aminomethylamination of Conjugated Dienes with Aminals Enabled by Chiral Palladium Complex-Catalyzed C-N Bond Activation.
Liu, Yang; Xie, Yinjun; Wang, Hongli; Huang, Hanmin; Journal of the American Chemical Society 138 (2016) 4314–4317; doi:10.1021/jacs.6b00976

data_4130160
_publ_section_title
;
 Enantioselective Aminomethylamination of Conjugated Dienes with Aminals
 Enabled by Chiral Palladium Complex-Catalyzed C-N Bond Activation.
;
_journal_issue                   13
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4314
_journal_page_last               4317
_journal_paper_doi               10.1021/jacs.6b00976
_journal_volume                  138
_journal_year                    2016
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C41 H42 Cl4 N2 O2'
_chemical_formula_sum            'C41 H42 Cl4 N2 O2'
_chemical_formula_weight         736.56
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-01-18
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                78.649(9)
_cell_angle_beta                 72.073(8)
_cell_angle_gamma                77.763(9)
_cell_formula_units_Z            2
_cell_length_a                   11.208(6)
_cell_length_b                   13.107(6)
_cell_length_c                   14.164(7)
_cell_measurement_reflns_used    2316
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      23.17
_cell_measurement_theta_min      2.71
_cell_volume                     1915.3(17)
_computing_cell_refinement       'Bruker SMART'
_computing_data_collection       'Bruker SMART APEX II'
_computing_data_reduction        'Bruker SMART'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.964
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0261
_diffrn_reflns_av_unetI/netI     0.0694
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            11278
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.103
_diffrn_reflns_theta_min         1.526
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.346
_exptl_absorpt_correction_T_max  0.9340
_exptl_absorpt_correction_T_min  0.9340
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.277
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             772
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.239
_refine_diff_density_min         -0.316
_refine_diff_density_rms         0.065
_refine_ls_abs_structure_details
;
 Refined as a perfect inversion twin.
;
_refine_ls_abs_structure_Flack   0.5
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.997
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     791
_refine_ls_number_reflns         9485
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      0.997
_refine_ls_R_factor_all          0.1188
_refine_ls_R_factor_gt           0.0594
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1096P)^2^+0.0370P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1582
_refine_ls_wR_factor_ref         0.2014
_reflns_Friedel_coverage         1.000
_reflns_Friedel_fraction_full    0.990
_reflns_Friedel_fraction_max     0.964
_reflns_number_gt                5375
_reflns_number_total             9485
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b00976_si_003.cif
_cod_data_source_block           1
_cod_original_cell_volume        1915.4(17)
_cod_database_code               4130160
_shelx_estimated_absorpt_t_max   0.934
_shelx_estimated_absorpt_t_min   0.934
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 N1(H1A), N2(H2A), N3(H3), N4(H4), C15(H15), C56(H56)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B),
 C25(H25A,H25B), C48(H48A,H48B), C49(H49A,H49B), C65(H65A,H65B), C66(H66A,H66B),
  C67(H67A,H67B), C74(H74A,H74B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3A), C2(H2), C5(H5), C1(H1), C10(H10), C11(H11), C13(H13), C9(H9),
 C20(H20), C21(H21), C23(H23), C24(H24), C30(H30), C29(H29), C27(H27), C28(H28),
  C32(H32), C33(H33), C35(H35), C38(H38), C39(H39), C46(H46), C45(H45),
 C43(H43), C42(H42), C51(H51), C52(H52), C54(H54), C55(H55), C57(H57), C58(H58),
  C60(H60), C61(H61), C64(H64), C69(H69), C70(H70), C72(H72), C73(H73),
 C76(H76), C77(H77), C79(H79), C78(H78)
2.d Fitted hexagon refined as free rotating group:
 C4(C3,C2,C6,C5,C1), C10(C11,C12,C13,C9,C14), C19(C20,C21,C22,C23,C24),
 C31(C30,C29,C26,C27,C28), C46(C45,C44,C43,C42,C47), C50(C51,C52,C53,C54,C55),
 C68(C69,C70,C71,C72,C73), C76(C77,C80,C79,C78,C75)
2.e Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C81(H81A,H81B,H81C), C82(H82A,H82B,
 H82C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'