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_4130161
_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         'C39 H40 N2'
_chemical_formula_sum            'C39 H40 N2'
_chemical_formula_weight         536.73
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 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                90
_cell_angle_beta                 101.641(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.346(8)
_cell_length_b                   9.780(3)
_cell_length_c                   12.743(4)
_cell_measurement_reflns_used    2063
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      20.22
_cell_measurement_theta_min      2.67
_cell_volume                     3215.9(17)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.995
_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  0.0325
_diffrn_reflns_av_unetI/netI     0.0581
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            8586
_diffrn_reflns_point_group_measured_fraction_full 0.860
_diffrn_reflns_point_group_measured_fraction_max 0.854
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.574
_diffrn_reflns_theta_min         1.578
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.064
_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    1.109
_exptl_crystal_description       block
_exptl_crystal_F_000             1152
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.252
_refine_diff_density_min         -0.221
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1044 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.1(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     334
_refine_ls_number_reflns         5153
_refine_ls_number_restraints     43
_refine_ls_restrained_S_all      1.136
_refine_ls_R_factor_all          0.1030
_refine_ls_R_factor_gt           0.0723
_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^)+(0.1175P)^2^+1.1695P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1942
_refine_ls_wR_factor_ref         0.2263
_reflns_Friedel_coverage         0.614
_reflns_Friedel_fraction_full    0.703
_reflns_Friedel_fraction_max     0.693
_reflns_number_gt                3456
_reflns_number_total             5153
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b00976_si_002.cif
_cod_data_source_block           1
_cod_original_cell_volume        3216.0(16)
_cod_database_code               4130161
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.981
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C36) \\sim Ueq, Uanis(C37) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C39) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C36)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C11) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C12) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
3.a Ternary CH refined with riding coordinates:
 C15(H15)
3.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C8(H8A,H8B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,H26B),
 C33(H33A,H33B)
3.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C6(H6), C5(H5), C4(H4), C3(H3), C10(H10), C11(H11), C12(H12),
 C13(H13), C14(H14), C16(H16), C17(H17), C19(H19), C20(H20), C21(H21), C22(H22),
  C23(H23), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32), C36(H36),
 C37(H37), C38(H38), C39(H39), C35(H35)
3.d Fitted hexagon refined as free rotating group:
 C2(C7,C6,C5,C4,C3), C9(C10,C11,C12,C13,C14), C36(C37,C38,C39,C34,C35)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'