Direct C-H Arylation of Thiophenes at Low Catalyst Loading of a Phosphine-Free Bis(alkoxo)palladium Complex.
Li, Yabo; Wang, Jingran; Huang, Mengmeng; Wang, Zhiwei; Wu, Yusheng; Wu, Yangjie; The Journal of organic chemistry 79 (2014) 2890–2897; doi:10.1021/jo402745b

data_4029260
_publ_section_title
;
 Direct C-H Arylation of Thiophenes at Low Catalyst Loading of a
 Phosphine-Free Bis(alkoxo)palladium Complex.
;
_journal_issue                   7
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              2890
_journal_page_last               2897
_journal_paper_doi               10.1021/jo402745b
_journal_volume                  79
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H18 O2 S'
_chemical_formula_sum            'C20 H18 O2 S'
_chemical_formula_weight         322.40
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-09-06
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 102.150(7)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   6.7761(5)
_cell_length_b                   11.2906(7)
_cell_length_c                   11.3537(8)
_cell_measurement_reflns_used    1678
_cell_measurement_temperature    291(2)
_cell_measurement_theta_max      72.1810
_cell_measurement_theta_min      5.5580
_cell_volume                     849.17(10)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      291.15
_diffrn_detector_area_resol_mean 16.2312
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -64.00  -37.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000 -180.0000 27

  2 omega  -64.00  -35.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000   90.0000 29

  3 omega  -41.00   30.00   1.0000    1.1300
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   37.0000 -120.0000 71

  4 omega -110.00  -28.00   1.0000    1.1300
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -57.0000  -30.0000 82

  5 omega  -87.00   -8.00   1.0000    1.1300
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  125.0000   60.0000 79

  6 omega  -32.00    7.00   1.0000    1.1300
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   30.0000  -30.0000 39

  7 omega  -13.00   44.00   1.0000    1.1300
omega____ theta____ kappa____ phi______ frames
    -       56.0000  -57.0000   30.0000 57

  8 omega   41.00   95.00   1.0000    1.1300
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000   30.0000 54

  9 omega   77.00  105.00   1.0000    1.1300
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -94.0000  -60.0000 28

 10 omega   44.00   87.00   1.0000    1.1300
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000 -180.0000 43

 11 omega   48.00   80.00   1.0000    1.1300
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000   90.0000 32

 12 omega   45.00   97.00   1.0000    1.1300
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000  -30.0000 52

 13 omega  110.00  177.00   1.0000    1.1300
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  120.0000 67

 14 omega   62.00   97.00   1.0000    1.1300
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -94.0000   60.0000 35

 15 omega   48.00   86.00   1.0000    1.1300
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000 -150.0000 38

 16 omega   51.00   90.00   1.0000    1.1300
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000  120.0000 39

 17 omega   82.00  108.00   1.0000    1.1300
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  120.0000 26

 18 omega  -77.00  -32.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000 -120.0000 45

 19 omega -113.00  -54.00   1.0000    1.1300
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000   90.0000 59

 20 omega -111.00  -21.00   1.0000    1.1300
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -61.0000 -180.0000 90
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0310035000
_diffrn_orient_matrix_UB_12      -0.0828807000
_diffrn_orient_matrix_UB_13      0.1100537000
_diffrn_orient_matrix_UB_21      0.0509742000
_diffrn_orient_matrix_UB_22      -0.1025758000
_diffrn_orient_matrix_UB_23      -0.0778711000
_diffrn_orient_matrix_UB_31      0.2249744000
_diffrn_orient_matrix_UB_32      0.0347887000
_diffrn_orient_matrix_UB_33      0.0327090000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0211
_diffrn_reflns_av_unetI/netI     0.0396
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            3267
_diffrn_reflns_theta_full        67.03
_diffrn_reflns_theta_max         67.03
_diffrn_reflns_theta_min         3.98
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.740
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57900
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour
;
;
_exptl_crystal_density_diffrn    1.261
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description
;
;
_exptl_crystal_F_000             340
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.158
_refine_diff_density_min         -0.146
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.01(2)
_refine_ls_extinction_coef       0.0083(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     218
_refine_ls_number_reflns         2259
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0429
_refine_ls_R_factor_gt           0.0376
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0516P)^2^+0.0341P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0938
_refine_ls_wR_factor_ref         0.0991
_reflns_number_gt                2048
_reflns_number_total             2259
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo402745b_si_003.cif
_cod_data_source_block           201309132
_cod_depositor_comments
;Adding full bibliography for
 ./tmp-cod-update-bibliographies-12971/cifs/4029260.cif.
;
_cod_original_cell_volume        849.18(10)
_cod_database_code               4029260
_chemical_oxdiff_formula         C20H20N4O4S1
_reflns_odcompleteness_completeness 99.88
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C19) = Uanis(C19A)
Uanis(C20) = Uanis(C20A)
3. Others
 Sof(C19A)=Sof(H19C)=Sof(H19D)=Sof(C20A)=Sof(H20C)=Sof(H20D)=1-FVAR(1)
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C20)=Sof(H20A)=Sof(H20B)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C20(H20A,H20B), C19A(H19C,H19D), C20A(H20C,H20D)
4.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C9(H9), C10(H10), C13(H13), C14(H14), C16(H16), C17(H17)
4.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C18(H18A,H18B,H18C)
;