Palladium-Catalyzed Dearomative syn-1,4-Carboamination.
Okumura, Mikiko; Shved, Alexander S.; Sarlah, David; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b11663

data_4126801
_publ_section_title
;
 Palladium-Catalyzed Dearomative syn-1,4-Carboamination.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b11663
_journal_year                    2017
_chemical_formula_moiety         '2(C22 H21 N3 O3), C H2 Cl2'
_chemical_formula_sum            'C45 H44 Cl2 N6 O6'
_chemical_formula_weight         835.76
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-10-24
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_cell_angle_alpha                109.1710(10)
_cell_angle_beta                 91.7910(10)
_cell_angle_gamma                101.3100(10)
_cell_formula_units_Z            2
_cell_length_a                   10.6521(4)
_cell_length_b                   12.9904(5)
_cell_length_c                   15.8802(7)
_cell_measurement_reflns_used    30260
_cell_measurement_temperature    99.99
_cell_measurement_theta_max      26.44
_cell_measurement_theta_min      2.27
_cell_volume                     2024.37(14)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      99.99
_diffrn_detector                 'Bruker Photon 100 area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'photon counter area detector'
_diffrn_measurement_device_type  'Bruker D8 Venture/Photon 100'
_diffrn_measurement_method       'profile data from \f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0403
_diffrn_reflns_av_unetI/netI     0.0224
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            56734
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.450
_diffrn_reflns_theta_min         2.270
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Siemens fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.219
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6994
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1270 before and 0.0540 after correction. The Ratio of minimum to maximum transmission is 0.9383. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.371
_exptl_crystal_description       prism
_exptl_crystal_F_000             876
_exptl_crystal_preparation       'Recrystalized from dichloromethane/pentane.'
_exptl_crystal_size_max          0.626
_exptl_crystal_size_mid          0.227
_exptl_crystal_size_min          0.206
_refine_diff_density_max         1.187
_refine_diff_density_min         -0.933
_refine_diff_density_rms         0.050
_refine_ls_extinction_coef       0.0239(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     617
_refine_ls_number_reflns         8332
_refine_ls_number_restraints     321
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0479
_refine_ls_R_factor_gt           0.0398
_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^)+(0.0293P)^2^+1.9156P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0885
_refine_ls_wR_factor_ref         0.0932
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7230
_reflns_number_total             8332
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b11663_si_003.cif
_cod_data_source_block           dd58gs
_cod_database_code               4126801
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.956
_shelx_estimated_absorpt_t_min   0.875
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups, All N(H) groups
2. Restrained distances
 C36-C37 \\sim C36-C37A
 with sigma of 0.01
 C37-C38 \\sim C37A-C38A
 with sigma of 0.01
 C37-O6 \\sim C37A-O6A
 with sigma of 0.01
 C43A-C38A \\sim C43A-C42A \\sim C43-C42 \\sim C42A-C41A \\sim C42-C41 \\sim
C41A-C40A \\sim C41-C40 ~
 C40-C39 \\sim C40A-C39A \\sim C39A-C38A \\sim C39-C38 \\sim C43-C38
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O6 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim
O6A \\sim C37A \\sim C38A \\sim C39A \\sim C40A \\sim C41A \\sim C42A \\sim
C43A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O6A \\sim O6: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 O6, C37, O6A, C37A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H36A)=Sof(O6A)=Sof(C37A)=Sof(C38A)=Sof(C39A)=Sof(H39A)=Sof(C40A)=
 Sof(H40A)=Sof(C41A)=Sof(H41A)=Sof(C42A)=Sof(H42A)=Sof(C43A)=Sof(H43A)=1-FVAR(1)
 Sof(H36)=Sof(O6)=Sof(C37)=Sof(C38)=Sof(C39)=Sof(H39)=Sof(C40)=Sof(H40)=
 Sof(C41)=Sof(H41)=Sof(C42)=Sof(H42)=Sof(C43)=Sof(H43)=FVAR(1)
 Sof(H35D)=Sof(H35E)=Sof(H35F)=1-FVAR(2)
 Sof(H35A)=Sof(H35B)=Sof(H35C)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C8(H8), C14(H14), C23(H23), C30(H30), C36(H36), C36(H36A)
6.b Secondary CH2 refined with riding coordinates:
 C45(H45A,H45B)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5A), C6(H6), C9(H9), C10(H10), C17(H17), C18(H18),
 C19(H19), C20(H20), C21(H21), C25(H25), C26(H26), C27(H27), C28(H28), C31(H31),
  C32(H32), C39(H39), C40(H40), C41(H41), C42(H42), C43(H43), C39A(H39A),
 C40A(H40A), C41A(H41A), C42A(H42A), C43A(H43A)
6.d Disordered Me refined as rotating group:
 C35(H35A,H35B,H35C,H35D,H35E,H35F)
6.e Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C22(H22A,H22B,H22C), C44(H44A,H44B,H44C)
;
_shelx_res_checksum              60230
_shelx_hkl_checksum              78747
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with spindle axis of 4 5 -3.'
_olex2_submission_original_sample_id naphthalene_propiophenone_MTAD
_olex2_submission_special_instructions 'No special instructions were received'