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_4130159
_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         '2(C77 H81 O2 P2 Pd), 2(Cl O4), C H2 Cl2'
_chemical_formula_sum            'C155 H164 Cl4 O12 P4 Pd2'
_chemical_formula_weight         2697.33
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-01-27
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.946(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   15.041(2)
_cell_length_b                   20.148(3)
_cell_length_c                   24.408(4)
_cell_measurement_reflns_used    9927
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      23.58
_cell_measurement_theta_min      2.31
_cell_volume                     7379.2(19)
_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 0.993
_diffrn_measured_fraction_theta_max 0.992
_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  0.0665
_diffrn_reflns_av_unetI/netI     0.0904
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            40333
_diffrn_reflns_point_group_measured_fraction_full 0.809
_diffrn_reflns_point_group_measured_fraction_max 0.804
_diffrn_reflns_theta_full        25.500
_diffrn_reflns_theta_max         26.022
_diffrn_reflns_theta_min         0.836
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.416
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            'clear dark yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.214
_exptl_crystal_description       block
_exptl_crystal_F_000             2820
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.872
_refine_diff_density_min         -0.463
_refine_diff_density_rms         0.066
_refine_ls_abs_structure_details
;
 Flack x determined using 5090 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.030(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.991
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1635
_refine_ls_number_reflns         23357
_refine_ls_number_restraints     170
_refine_ls_restrained_S_all      1.008
_refine_ls_R_factor_all          0.0811
_refine_ls_R_factor_gt           0.0589
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0893P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1505
_refine_ls_wR_factor_ref         0.1651
_reflns_Friedel_coverage         0.574
_reflns_Friedel_fraction_full    0.612
_reflns_Friedel_fraction_max     0.604
_reflns_number_gt                17106
_reflns_number_total             23357
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b00976_si_005.cif
_cod_data_source_block           1
_cod_original_cell_volume        7379.6(19)
_cod_database_code               4130159
_platon_squeeze_void_probe_radius 1.20
_shelx_estimated_absorpt_t_max   0.903
_shelx_estimated_absorpt_t_min   0.892
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C154-C155
 1.44 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C122) \\sim Ueq, Uanis(C121) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C14)
\\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C43) \\sim Ueq,
Uanis(C44) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O11) \\sim Ueq, Uanis(O12) \\sim Ueq, Uanis(O9) \\sim Ueq, Uanis(O10)
\\sim Ueq, Uanis(O6) \\sim Ueq, Uanis(O5) \\sim Ueq, Uanis(O8) \\sim Ueq,
Uanis(O7) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C154) \\sim Ueq: with sigma of 0.021 and sigma for terminal atoms of 0.01
Uanis(C154) \\sim Ueq, Uanis(C2AA) \\sim Ueq, Uanis(C153) \\sim Ueq,
Uanis(C155) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C77) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C78) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C47) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.05
Uanis(C48') \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C46') \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C48) \\sim Ueq, Uanis(C48') \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Fixed Sof: H47A(0.5) H47(0.5) H15A(0.65) H15B(0.65) H15C(0.35) H15D(0.35)
 H15E(0.65) H15F(0.65) H15G(0.35) H15H(0.35) C154(0.65) H154(0.65) C2AA(0.35)
 H2AA(0.35) C48'(0.5) H48A(0.5) H48B(0.5) H48C(0.5) C46'(0.5) H46A(0.5)
 H46B(0.5) H46C(0.5) C46(0.5) H46D(0.5) H46E(0.5) H46F(0.5) C48(0.5) H48D(0.5)
 H48E(0.5) H48F(0.5)
5.a Ternary CH refined with riding coordinates:
 C8(H8), C11(H11), C15(H15), C43(H43), C47(H47A), C47(H47), C49(H49), C77(H77),
  C85(H85), C88(H88), C91(H91), C120(H120), C123(H123), C126(H126), C154(H154),
 C2AA(H2AA)
5.b Secondary CH2 refined with riding coordinates:
 C76(H76A,H76B), C78(H78A,H78B), C153(H15A,H15B), C153(H15C,H15D), C155(H15E,
 H15F), C155(H15G,H15H), C156(H15I,H15J)
5.c Aromatic/amide H refined with riding coordinates:
 C4AA(H4AA), C5(H5), C18(H18), C23(H23), C24(H24), C25(H25), C26(H26),
 C29(H29), C30(H30), C31(H31), C32(H32), C34(H34), C39(H39), C41(H41), C53(H53),
  C54(H54), C55(H55), C56(H56), C57(H57), C58(H58), C59(H59), C60(H60),
 C61(H61), C63(H63), C65(H65), C66(H66), C67(H67), C68(H68), C69(H69), C75(H75),
  C74(H74), C73(H73), C72(H72), C71(H71), C81(H81), C83(H83), C95(H95),
 C100(H100), C101(H101), C102(H102), C103(H103), C106(H106), C107(H107),
 C108(H108), C109(H109), C111(H111), C116(H116), C118(H118), C130(H130),
 C131(H131), C132(H132), C133(H133), C134(H134), C136(H136), C137(H137),
 C138(H138), C139(H139), C140(H140), C141(H141), C142(H142), C143(H143),
 C144(H144), C145(H145), C147(H147), C149(H149), C150(H150), C151(H151),
 C152(H152)
5.d Fitted hexagon refined as free rotating group:
 C75(C74,C73,C72,C71,C70)
5.e Idealised Me refined as rotating group:
 C1AA(H1AA,H1AB,H1AC), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C13(H13A,H13B,
 H13C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C44(H44A,H44B,H44C), C45(H45A,
 H45B,H45C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C86(H86A,H86B,H86C),
 C87(H87A,H87B,H87C), C89(H89A,H89B,H89C), C90(H90A,H90B,H90C), C92(H92A,H92B,
 H92C), C93(H93A,H93B,H93C), C121(H12D,H12E,H12F), C122(H12G,H12H,H12I),
 C124(H12J,H12K,H12L), C125(H12M,H12N,H12O), C127(H12P,H12Q,H12R), C128(H12S,
 H12T,H12U), C48'(H48A,H48B,H48C), C46'(H46A,H46B,H46C), C46(H46D,H46E,H46F),
 C48(H48D,H48E,H48F)
;
_shelx_res_checksum              31778
_shelx_hkl_checksum              86817
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'