Transfer hydrogenative para-selective aminoalkylation of aniline derivatives with N-heteroarenes via ruthenium/acid dual catalysis.
Chen, Xiuwen; Zhao, He; Chen, Chunlian; Jiang, Huanfeng; Zhang, Min; Chemical communications (Cambridge, England) 54 (2018) 9087–9090; doi:10.1039/c8cc04233k

data_7122009
_publ_section_title
;
 Transfer hydrogenative para-selective aminoalkylation of aniline
 derivatives with N-heteroarenes via ruthenium/acid dual catalysis.
;
_journal_issue                   65
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              9087
_journal_page_last               9090
_journal_paper_doi               10.1039/c8cc04233k
_journal_volume                  54
_journal_year                    2018
_chemical_formula_moiety         'C23 H22 Cl N3'
_chemical_formula_sum            'C23 H22 Cl N3'
_chemical_formula_weight         375.89
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_block_doi                 10.5517/ccdc.csd.cc1yxhn0
_audit_creation_date             2017-07-29
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2017.07.20 svn.r3457 for OlexSys, GUI svn.r5370)
;
_audit_update_record
;
2018-01-05 deposited with the CCDC.
2018-07-23 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 119.191(9)
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   33.350(13)
_cell_length_b                   5.917(2)
_cell_length_c                   21.754(10)
_cell_measurement_reflns_used    1290
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      18.42
_cell_measurement_theta_min      2.56
_cell_volume                     3748(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.960
_diffrn_measured_fraction_theta_max 0.960
_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  0.0967
_diffrn_reflns_av_unetI/netI     0.0933
_diffrn_reflns_limit_h_max       42
_diffrn_reflns_limit_h_min       -42
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            19411
_diffrn_reflns_theta_full        27.62
_diffrn_reflns_theta_max         27.62
_diffrn_reflns_theta_min         1.91
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.217
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.6344
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0653 before and 0.0474 after correction.
The Ratio of minimum to maximum transmission is 0.8510.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.333
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1584
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.29
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.619
_refine_diff_density_min         -0.322
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.997
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     251
_refine_ls_number_reflns         4195
_refine_ls_number_restraints     31
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.2094
_refine_ls_R_factor_gt           0.0936
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1535P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2339
_refine_ls_wR_factor_ref         0.3013
_reflns_number_gt                1690
_reflns_number_total             4195
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c8cc04233k2.cif
_cod_data_source_block           1
_cod_depositor_comments          'Adding full bibliography for 7122009.cif.'
_cod_original_cell_volume        3747(3)
_cod_database_code               7122009
_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, All N(H) groups,
  All N(H,H) groups
2. Restrained distances
 C6-H6
 0.93 with sigma of 0.02
 C8-N19
 1.337 with sigma of 0.02
 N19-C25
 1.337 with sigma of 0.02
 C25-C26
 1.406 with sigma of 0.02
 C26-C23
 1.458 with sigma of 0.02
 C26-C25
 1.37 with sigma of 0.002
 C1B-C1A
 0.85 with sigma of 0.02
 C1A-H1A
 0.96 with sigma of 0.02
 H1A-H21
 1.98 with sigma of 0.02
 H1B-H20
 1.98 with sigma of 0.02
 H20-H1B
 1.98 with sigma of 0.02
3. Rigid bond restraints
 N19
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C25, C26
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C17, C20
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C25) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C23) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C1B) = Uanis(C1A)
5. Others
 Sof(H5B)=Sof(H22C)=Sof(H22D)=Sof(C1A)=Sof(H1A)=1-FVAR(1)
 Sof(H5A)=Sof(H22A)=Sof(H22B)=Sof(C1B)=Sof(H1B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C1A(H1A), C1B(H1B)
6.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C22(H22C,H22D), C22(H22A,H22B), C23(H23A,H23B), C25(H25A,
 H25B), C26(H26A,H26B)
6.c Aromatic/amide H refined with riding coordinates:
 N5(H5A), N5(H5B), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12), C14(H14),
 C15(H15), C20(H20), C21(H21)
;
_olex2_submission_special_instructions 'No special instructions were received'