Palladium-catalyzed primary amine-directed regioselective mono- and di-alkynylation of biaryl-2-amines.
Jiang, Guangbin; Hu, Weigao; Li, Jianxiao; Zhu, Chuanle; Wu, Wanqing; Jiang, Huanfeng; Chemical communications (Cambridge, England) 54 (2018) 1746–1749; doi:10.1039/c7cc09308j

data_7121170
_publ_section_title
;
 Palladium-catalyzed primary amine-directed regioselective mono- and
 di-alkynylation of biaryl-2-amines.
;
_journal_issue                   14
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              1746
_journal_page_last               1749
_journal_paper_doi               10.1039/c7cc09308j
_journal_volume                  54
_journal_year                    2018
_chemical_formula_moiety         'C33 H35 N Si'
_chemical_formula_sum            'C33 H35 N Si'
_chemical_formula_weight         473.71
_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             2017-06-09
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2017-07-07 deposited with the CCDC.
2018-01-22 downloaded from the CCDC.
;
_cell_angle_alpha                98.702(4)
_cell_angle_beta                 99.193(4)
_cell_angle_gamma                99.700(4)
_cell_formula_units_Z            4
_cell_length_a                   9.0089(6)
_cell_length_b                   13.9567(6)
_cell_length_c                   22.3783(10)
_cell_measurement_reflns_used    7053
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      29.1560
_cell_measurement_theta_min      3.8980
_cell_volume                     2691.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.833
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     13.00  91.00   1.00    8.00    --   11.74  19.00 -90.00   78
  2  \w      3.00  53.00   1.00    8.00    --   11.74 -99.00   0.00   50
  3  \w     65.00  90.00   1.00    8.00    --   11.74-178.00 -30.00   25
  4  \w     -8.00  32.00   1.00    8.00    --  -11.51-111.00 -24.00   40
  5  \w    -31.00  -5.00   1.00    8.00    --   11.74 -37.00-180.00   26
  6  \w    -57.00 -31.00   1.00    8.00    --  -11.51 111.00  68.00   26
  7  \w    -68.00  43.00   1.00    8.00    --   11.74 -19.00  90.00  111
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0472908000
_diffrn_orient_matrix_UB_12      -0.0128134000
_diffrn_orient_matrix_UB_13      -0.0296994000
_diffrn_orient_matrix_UB_21      0.0592191000
_diffrn_orient_matrix_UB_22      -0.0194838000
_diffrn_orient_matrix_UB_23      -0.0119898000
_diffrn_orient_matrix_UB_31      -0.0295961000
_diffrn_orient_matrix_UB_32      -0.0469760000
_diffrn_orient_matrix_UB_33      0.0063957000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0364
_diffrn_reflns_av_unetI/netI     0.0755
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.833
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            25384
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.833
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.544
_diffrn_reflns_theta_min         3.315
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.109
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82289
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.169
_exptl_crystal_description       block
_exptl_crystal_F_000             1016
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.190
_refine_diff_density_min         -0.617
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     651
_refine_ls_number_reflns         12544
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.1029
_refine_ls_R_factor_gt           0.0728
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0714P)^2^+3.2067P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1708
_refine_ls_wR_factor_ref         0.1909
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9034
_reflns_number_total             12544
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7cc09308j2.cif
_cod_data_source_block           exp_636
_cod_depositor_comments
'Adding full bibliography for 7121170--7121171.cif.'
_cod_database_code               7121170
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.989
_shelx_estimated_absorpt_t_min   0.985
_reflns_odcompleteness_completeness 99.75
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C015, N01R, C01M
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C015 \\sim N01R \\sim C01M: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
4.a Ternary CH refined with riding coordinates:
 C00Z(H00Z), C010(H010), C016(H016), C25(H25), C31(H31), C28(H28)
4.b Aromatic/amide H refined with riding coordinates:
 C00E(H00E), C00G(H00G), C00J(H00J), C2(H2), C4(H4), C14(H14), C00R(H00R),
 C00S(H00S), C5(H5), C15(H15), C00Y(H00Y), C012(H012), C18(H18), C7(H7),
 C018(H018), C8(H8), C9(H9), C19(H19), C21(H21), C20(H20), C01O(H01S),
 C01W(H01W), C01X(H01X), C01Y(H01Y)
4.c X=CH2 refined with riding coordinates:
 N01R(H01T,H01U)
4.d Idealised Me refined as rotating group:
 C01A(H01A,H01B,H01C), C01F(H01D,H01E,H01F), C01G(H01G,H01H,H01I), C01H(H01J,
 H01K,H01L), C01K(H01M,H01N,H01O), C01N(H01P,H01Q,H01R), C30(H30A,H30B,H30C),
 C26(H26A,H26B,H26C), C29(H29A,H29B,H29C), C33(H33A,H33B,H33C), C27(H27A,H27B,
 H27C), C32(H32A,H32B,H32C)
;
_shelx_res_checksum              22210
_olex2_date_sample_data_collection 2017-06-09
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.809
_oxdiff_exptl_absorpt_empirical_full_min 0.506