Visible-light-induced difunctionalization of alkynes: The synthesis of thiazoles and 1,1-dibromo-1-en-3-ynes.
Huang, Xiaoying; Chen, Hui; Huang, Zhongzhi; Xu, Yan-Li; Li, Fangyao; Ma, Xian-Li; Chen, Yan-Yan; The Journal of organic chemistry  (2019) –; doi:10.1021/acs.joc.9b02300

data_4036097
_publ_section_title
;
 Visible-light-induced difunctionalization of alkynes: The synthesis of
 thiazoles and 1,1-dibromo-1-en-3-ynes.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.9b02300
_journal_year                    2019
_chemical_formula_moiety         'C16 H8 Br2 F2'
_chemical_formula_sum            'C16 H8 Br2 F2'
_chemical_formula_weight         398.04
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-12-20
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.198(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   3.9499(4)
_cell_length_b                   15.0724(18)
_cell_length_c                   23.358(3)
_cell_measurement_reflns_used    1798
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      26.7860
_cell_measurement_theta_min      2.6920
_cell_volume                     1389.6(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 0.999
_diffrn_measured_fraction_theta_max 0.999
_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      3.00  29.00   1.00    5.00    --  -11.59 -99.00-180.00   26
  2  \w    -80.00   9.00   1.00    5.00    --  -11.59 -37.00 -90.00   89
  3  \w    -31.00  59.00   1.00    5.00    --  -11.59  37.00  90.00   90
;
_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      0.0437426000
_diffrn_orient_matrix_UB_12      -0.0383772000
_diffrn_orient_matrix_UB_13      -0.0156724000
_diffrn_orient_matrix_UB_21      -0.0149922000
_diffrn_orient_matrix_UB_22      0.0245504000
_diffrn_orient_matrix_UB_23      -0.0258838000
_diffrn_orient_matrix_UB_31      0.1735866000
_diffrn_orient_matrix_UB_32      0.0118147000
_diffrn_orient_matrix_UB_33      0.0028760000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0528
_diffrn_reflns_av_unetI/netI     0.0764
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       4
_diffrn_reflns_limit_h_min       -4
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            5933
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         2.207
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    5.841
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48950
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.903
_exptl_crystal_description       block
_exptl_crystal_F_000             768
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.096
_refine_diff_density_min         -1.537
_refine_diff_density_rms         0.187
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     181
_refine_ls_number_reflns         2456
_refine_ls_number_restraints     21
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0890
_refine_ls_R_factor_gt           0.0707
_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^)+(0.0252P)^2^+25.0609P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1327
_refine_ls_wR_factor_ref         0.1411
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2026
_reflns_number_total             2456
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02300_si_002.cif
_cod_data_source_block           10-16-4b
_cod_database_code               4036097
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.593
_shelx_estimated_absorpt_t_min   0.541
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Rigid bond restraints
 C1, C2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C9, C16
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C5, C6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C1 \\sim C2: within 2A with sigma of 0.002 and sigma for terminal atoms of 0.004
C9 \\sim C16: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004
C5 \\sim C6: within 2A with sigma of 0.002 and sigma for terminal atoms of 0.004
4.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C11(H11), C3(H3), C12(H12), C15(H15), C5(H5), C14(H14)
;
_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 1.519
_oxdiff_exptl_absorpt_empirical_full_min 0.723