Visible-light-mediated direct difluoromethylation of alkynoates: Synthesis of 3-difluoromethylated coumarins
Zhu, Mei; Fu, Weijun; Wang, Zhiqiang; Xu, Chen; Ji, Baoming; Org. Biomol. Chem.  (2017) –; doi:10.1039/C7OB02366A

data_7155926
_publ_section_title
;
 Visible-light-mediated direct difluoromethylation of alkynoates:
 Synthesis of 3-difluoromethylated coumarins
;
_journal_name_full               'Org. Biomol. Chem.'
_journal_paper_doi               10.1039/C7OB02366A
_journal_year                    2017
_chemical_formula_moiety         'C17 H12 F2 O2'
_chemical_formula_sum            'C17 H12 F2 O2'
_chemical_formula_weight         286.27
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-05-26
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2017-09-07 deposited with the CCDC.
2017-10-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.833(8)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.9567(6)
_cell_length_b                   26.208(2)
_cell_length_c                   11.6346(9)
_cell_measurement_reflns_used    3934
_cell_measurement_temperature    291.8(5)
_cell_measurement_theta_max      24.2880
_cell_measurement_theta_min      3.8710
_cell_volume                     2855.9(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41r (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41r (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41r (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      air
_diffrn_ambient_temperature      291.8(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0584
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.945
_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    -20.00  29.00   1.00   38.96    --   -9.62 -99.00 120.00   49
  2  \w    -26.00  58.00   1.00   38.96    --   -9.62  57.00-150.00   84
  3  \w    -77.00   5.00   1.00   38.96    --   -9.62 -38.00   0.00   82
  4  \w    -19.00  10.00   1.00   38.96    --   -9.62 -99.00-120.00   29
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0675246000
_diffrn_orient_matrix_UB_12      0.0009626000
_diffrn_orient_matrix_UB_13      0.0079015000
_diffrn_orient_matrix_UB_21      -0.0099840000
_diffrn_orient_matrix_UB_22      0.0252278000
_diffrn_orient_matrix_UB_23      -0.0235237000
_diffrn_orient_matrix_UB_31      -0.0327274000
_diffrn_orient_matrix_UB_32      -0.0098518000
_diffrn_orient_matrix_UB_33      -0.0597812000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0383
_diffrn_reflns_av_unetI/netI     0.0518
_diffrn_reflns_Laue_measured_fraction_full 0.945
_diffrn_reflns_Laue_measured_fraction_max 0.945
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            13250
_diffrn_reflns_point_group_measured_fraction_full 0.945
_diffrn_reflns_point_group_measured_fraction_max 0.945
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         3.398
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.104
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83546
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41r (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.332
_exptl_crystal_description       block
_exptl_crystal_F_000             1184
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.341
_refine_diff_density_min         -0.202
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     381
_refine_ls_number_reflns         4747
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.1060
_refine_ls_R_factor_gt           0.0663
_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^)+(0.0690P)^2^+1.1210P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1567
_refine_ls_wR_factor_ref         0.1711
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2996
_reflns_number_total             4747
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob02366a2.cif
_cod_data_source_block           exp_579
_cod_database_code               7155926
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 99.60
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     23.21
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1), C18(H18)
2.b Aromatic/amide H refined with riding coordinates:
 C13(H13), C22(H22), C16(H16), C17(H17), C10(H10), C34(H34), C26(H26),
 C25(H25), C8(H8), C6(H6), C9(H9), C30(H30), C32(H32), C33(H33), C7(H7),
 C31(H31)
2.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C24(H24A,H24B,H24C)
;
_olex2_date_sample_data_collection 2017-05-20
_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 1.342
_oxdiff_exptl_absorpt_empirical_full_min 0.826