Room-temperature Pd(ii)-catalyzed direct C–H TIPS-ethynylation of phenylacetic amides with terminal alkynes
Chen, Cui-Hong; Chai, Yun; Zhou, Zheng-Xin; Rao, Wei-Hao; Liu, Bin; Liu, Li; Xu, Ran; Liu, Yue-Jin; Zeng, Ming-Hua; Organic Chemistry Frontiers 6 (2019) 442–; doi:10.1039/C8QO01215F

data_1554539
_publ_section_title
;
 Room-temperature Pd(ii)-catalyzed direct C--H TIPS-ethynylation of
 phenylacetic amides with terminal alkynes
;
_journal_issue                   4
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              442
_journal_paper_doi               10.1039/C8QO01215F
_journal_volume                  6
_journal_year                    2019
_chemical_formula_moiety         'C34 H44 N2 O Si'
_chemical_formula_sum            'C34 H44 N2 O Si'
_chemical_formula_weight         524.80
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2018-11-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-11-08 deposited with the CCDC.
2018-12-11 downloaded from the CCDC.
;
_cell_angle_alpha                100.993(2)
_cell_angle_beta                 95.022(2)
_cell_angle_gamma                92.933(2)
_cell_formula_units_Z            2
_cell_length_a                   8.8134(2)
_cell_length_b                   10.3559(3)
_cell_length_c                   18.0350(4)
_cell_measurement_reflns_used    8244
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      76.3270
_cell_measurement_theta_min      2.4920
_cell_volume                     1605.78(7)
_computing_cell_refinement       'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.945
_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    -16.00  14.00   0.50    0.05    --   43.80 -57.00 -30.00   60
  2  \w     40.00  83.00   0.50    0.05    --   43.80-118.00  15.00   86
  3  \w     82.00 114.00   0.50    0.12    --  111.75-118.00  15.00   64
  4  \w     48.00 134.00   0.50    0.12    --  111.75 -30.00 120.00  172
  5  \w    104.00 133.00   0.50    0.12    --  111.75 -45.00 150.00   58
  6  \w    142.00 178.00   0.50    0.12    --  111.75  30.00  90.00   72
  7  \w    140.00 178.00   0.50    0.12    --  111.75  77.00  90.00   76
  8  \w    113.00 138.00   0.50    0.12    --  111.75 118.00 102.00   50
  9  \w     95.00 176.00   0.50    0.12    --  111.75 125.00 150.00  162
 10  \w    114.00 140.00   0.50    0.12    --  111.75  30.00  90.00   52
 11  \w     83.00 133.00   0.50    0.12    --  111.75  77.00  90.00  100
 12  \w     83.00 160.00   0.50    0.12    --  111.75  77.00 -30.00  154
 13  \w     88.00 178.00   0.50    0.12    --  111.75  61.00-180.00  180
 14  \w     76.00 101.00   0.50    0.05    --   43.80 159.00-104.00   50
 15  \w     76.00 122.00   0.50    0.05    --   43.80 178.00   0.00   92
 16  \w     73.00 163.00   0.50    0.12    --  111.75 159.00-104.00  180
 17  \w     69.00  95.00   0.50    0.12    --  111.75 -45.00 150.00   52
 18  \w     40.00 108.00   0.50    0.12    --  111.75 -94.00  60.00  136
 19  \w     41.00 119.00   0.50    0.12    --  111.75-125.00 -30.00  156
 20  \w    114.00 139.00   0.50    0.12    --  111.75-159.00-136.00   50
 21  \w     69.00 119.00   0.50    0.05    --   43.80-159.00-136.00  100
 22  \w     79.00 105.00   0.50    0.12    --  111.75 -94.00-120.00   52
 23  \w     49.00  79.00   0.50    0.12    --  111.75-118.00  15.00   60
 24  \w     40.00  71.00   0.50    0.12    --  111.75 -94.00-120.00   62
 25  \w     56.00  98.00   0.50    0.12    --  111.75 -94.00-150.00   84
 26  \w     39.00  64.00   0.50    0.12    --  111.75-125.00 150.00   50
 27  \w    -81.00 -50.00   0.50    0.05    --  -43.80-159.00-136.00   62
 28  \w   -103.00 -78.00   0.50    0.12    --  -90.25-159.00-136.00   50
 29  \w   -118.00 -20.00   0.50    0.05    --  -43.80 -77.00-150.00  196
 30  \w    -69.00  33.00   0.50    0.05    --  -43.80  19.00   0.00  204
 31  \w    -52.00 -17.00   0.50    0.12    --  -90.25 118.00 102.00   70
 32  \w    -61.00 -36.00   0.50    0.05    --  -43.80 118.00 102.00   50
 33  \w    -91.00 -58.00   0.50    0.12    --  -90.25 118.00 102.00   66
 34  \w    -98.00 -60.00   0.50    0.05    --  -43.80 159.00-104.00   76
 35  \w    -88.00 -61.00   0.50    0.12    --  -90.25 -77.00  90.00   54
 36  \w   -145.00-120.00   0.50    0.12    --  -90.25-118.00  15.00   50
 37  \w   -148.00-112.00   0.50    0.12    --  -90.25 -77.00  90.00   72
 38  \w   -162.00 -83.00   0.50    0.12    --  -90.25 -94.00 -60.00  158
 39  \w   -101.00 -75.00   0.50    0.12    --  -90.25 159.00-104.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0125917000
_diffrn_orient_matrix_UB_12      0.1128560000
_diffrn_orient_matrix_UB_13      -0.0442575000
_diffrn_orient_matrix_UB_21      -0.0555308000
_diffrn_orient_matrix_UB_22      -0.0972106000
_diffrn_orient_matrix_UB_23      -0.0744123000
_diffrn_orient_matrix_UB_31      -0.1664230000
_diffrn_orient_matrix_UB_32      0.0298339000
_diffrn_orient_matrix_UB_33      0.0123075000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0392
_diffrn_reflns_av_unetI/netI     0.0437
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.945
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            17410
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.945
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.816
_diffrn_reflns_theta_min         2.508
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.835
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64525
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.34b (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.085
_exptl_crystal_description       block
_exptl_crystal_F_000             568
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.147
_refine_diff_density_min         -0.404
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.199
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     349
_refine_ls_number_reflns         6387
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.199
_refine_ls_R_factor_all          0.0943
_refine_ls_R_factor_gt           0.0837
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2634
_refine_ls_wR_factor_ref         0.2881
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5154
_reflns_number_total             6387
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8qo01215f2.cif
_cod_data_source_block           hubu-lyj-cch-1-64-5
_cod_database_code               1554539
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C N H O'
_shelx_estimated_absorpt_t_max   0.921
_shelx_estimated_absorpt_t_min   0.788
_reflns_odcompleteness_completeness 99.13
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C30-C29 = C31-C29
 1.51 with sigma of 0.005
3. Rigid bond restraints
 C29, C30
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4.a Ternary CH refined with riding coordinates:
 C11(H11), C12(H12), C26(H26), C29(H29), C32(H32)
4.b Secondary CH2 refined with riding coordinates:
 C13(H13a,H13b), C14(H14a,H14b), C15(H15a,H15b), C16(H16a,H16b), C17(H17a,H17b)
4.c Aromatic/amide H refined with riding coordinates:
 N2(H2), C1(H1), C2(H2a), C3(H3), C5(H5), C6(H6), C7(H7), C19(H19), C20(H20),
 C21(H21), C22(H22)
4.d Idealised Me refined as rotating group:
 C00X(H00a,H00b,H00c), C28(H28a,H28b,H28c), C30(H30a,H30b,H30c), C31(H31a,H31b,
 H31c), C33(H33a,H33b,H33c), C34(H34a,H34b,H34c)
;
_shelx_res_checksum              53477
_shelx_hkl_checksum              285
_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 2.656
_oxdiff_exptl_absorpt_empirical_full_min 0.642