Palladium-Catalyzed Template Directed C-5 Selective Olefination of Thiazoles.
Achar, Tapas Kumar; Biswas, Jyoti Prasad; Porey, Sandip; Pal, Tapas; Ramakrishna, Kankanala; Maiti, Siddhartha; Maiti, Debabrata; The Journal of organic chemistry 84 (2019) 8315–8321; doi:10.1021/acs.joc.9b01074

data_4034655
_publ_section_title
;
 Palladium-Catalyzed Template Directed C-5 Selective Olefination of
 Thiazoles.
;
_journal_issue                   12
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              8315
_journal_page_last               8321
_journal_paper_doi               10.1021/acs.joc.9b01074
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C42 H31 F2 N7 O2 Pd, C H2 Cl2'
_chemical_formula_sum            'C43 H33 Cl2 F2 N7 O2 Pd'
_chemical_formula_weight         895.06
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-29
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.165(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.7124(4)
_cell_length_b                   28.1168(10)
_cell_length_c                   15.7854(5)
_cell_measurement_reflns_used    9138
_cell_measurement_temperature    150
_cell_measurement_theta_max      30.5800
_cell_measurement_theta_min      2.3480
_cell_volume                     3856.7(3)
_computing_cell_refinement
'CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)'
_computing_data_collection
'CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)'
_computing_data_reduction
'CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)'
_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_temperature      150
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -85.00  70.00   0.50    8.00    --  -20.00   0.00-108.00  310
  2  \w    -59.00  20.50   0.50    8.00    --  -20.00  72.00 -36.00  159
  3  \w    -38.50  -0.50   0.50    8.00    --  -20.00 -72.00  36.00   76
  4  \w    -30.00 -23.50   0.50    8.00    --  -20.00 -72.00-180.00   13
;
_diffrn_measurement_device       'AFC12 (Right): Kappa 3 circle'
_diffrn_measurement_device_type  'Rigaku Saturn724+ (2x2 bin mode)'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0317640000
_diffrn_orient_matrix_UB_12      -0.0216944000
_diffrn_orient_matrix_UB_13      0.0161143000
_diffrn_orient_matrix_UB_21      0.0621686000
_diffrn_orient_matrix_UB_22      0.0126633000
_diffrn_orient_matrix_UB_23      0.0208673000
_diffrn_orient_matrix_UB_31      -0.0422785000
_diffrn_orient_matrix_UB_32      0.0023355000
_diffrn_orient_matrix_UB_33      0.0365350000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0594
_diffrn_reflns_av_unetI/netI     0.0682
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            19999
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        24.997
_diffrn_reflns_theta_max         24.997
_diffrn_reflns_theta_min         2.344
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.678
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86396
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.542
_exptl_crystal_description       block
_exptl_crystal_F_000             1816
_exptl_crystal_size_max          0.189
_exptl_crystal_size_mid          0.085
_exptl_crystal_size_min          0.047
_refine_diff_density_max         0.512
_refine_diff_density_min         -0.614
_refine_diff_density_rms         0.107
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     518
_refine_ls_number_reflns         6791
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0644
_refine_ls_R_factor_gt           0.0471
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0392P)^2^+4.0337P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0987
_refine_ls_wR_factor_ref         0.1102
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5394
_reflns_number_total             6791
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b01074_si_006.cif
_cod_data_source_block           dm-ta-t7-dmap_mo
_cod_database_code               4034655
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 88.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     31.02
_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.a Secondary CH2 refined with riding coordinates:
 C01L(H01p,H01q)
2.b Aromatic/amide H refined with riding coordinates:
 C00E(H00E), C00I(H00I), C00J(H00J), C00K(H00K), C00L(H00L), C00U(H00U),
 C00V(H00V), C00X(H00X), C00Y(H00Y), C010(H010), C012(H012), C015(H015),
 C016(H016), C01B(H01g), C01D(H01k), C01F(H01l), C01I(H01m), C01J(H01n),
 C01K(H01o)
2.c Idealised Me refined as rotating group:
 C00Z(H00a,H00b,H00c), C013(H01a,H01b,H01c), C014(H01d,H01e,H01f), C01C(H01h,
 H01i,H01j)
;
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.211
_oxdiff_exptl_absorpt_empirical_full_min 0.807