Carbene-controlled regioselectivity in photochemical cascades.
Di Filippo, Mara; Baumann, Marcus; Organic & biomolecular chemistry 21 (2023) 2930–2934; doi:10.1039/d3ob00122a

data_7159144
_publ_section_title
;
 Carbene-controlled regioselectivity in photochemical cascades.
;
_journal_issue                   14
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2930
_journal_page_last               2934
_journal_paper_doi               10.1039/d3ob00122a
_journal_volume                  21
_journal_year                    2023
_chemical_formula_moiety         'C22 H18 F2 O3'
_chemical_formula_sum            'C22 H18 F2 O3'
_chemical_formula_weight         368.36
_chemical_name_common            4B
_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     dual
_audit_creation_date             2022-06-11
_audit_creation_method
;
Olex2 1.5-ac5-021
(compiled 2022.02.15 svn.rf212a0ae for Rigaku Oxford Diffraction, GUI svn.r6439)
;
_audit_update_record
;
2022-08-15 deposited with the CCDC.	2023-02-01 downloaded from the CCDC.
;
_cell_angle_alpha                74.4540(10)
_cell_angle_beta                 77.6380(10)
_cell_angle_gamma                88.2870(10)
_cell_formula_units_Z            2
_cell_length_a                   7.80430(10)
_cell_length_b                   7.92550(10)
_cell_length_c                   14.73430(10)
_cell_measurement_reflns_used    19253
_cell_measurement_temperature    100.55(10)
_cell_measurement_theta_max      76.0780
_cell_measurement_theta_min      5.7840
_cell_volume                     857.296(17)
_computing_cell_refinement       'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-ac5-021 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-021 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.55(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3196
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.990
_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   -110.00 -59.00   0.30    0.30    --  -38.50-152.00 152.00  170
  2  \w    -85.00  -2.80   0.30    0.30    --  -38.50 121.00  35.00  274
  3  \w   -106.00 -20.80   0.30    0.30    --  -38.50 152.00-165.00  284
  4  \w     24.00  96.00   0.30    0.30    --   43.37-121.00 -48.00  240
  5  \w     41.00 116.00   0.30    0.30    --   43.37-152.00 152.00  250
  6  \w     39.00 111.00   0.30    0.40    --  111.00-121.00 -48.00  240
  7  \w     81.00 163.20   0.30    0.40    --  111.00 152.00-165.00  274
  8  \w     41.00 131.00   0.30    0.40    --  111.00-152.00 152.00  300
  9  \w     99.00 177.00   0.30    0.40    --  111.00 121.00  35.00  260
 10  \w     -2.00  23.20   0.30    0.30    --   34.00  91.00-112.92   84
 11  \w   -110.00  -9.80   0.30    0.30    --  -38.50 -68.00  45.81  334
 12  \w   -111.00 -16.80   0.30    0.30    --  -38.50 -37.00-150.00  314
 13  \w     12.00  42.00   0.30    0.30    --   43.37  78.00  23.25  100
 14  \w     14.00  41.00   0.30    0.30    --   46.00  81.00 -56.64   90
 15  \w     13.00  40.90   0.30    0.30    --   46.00  82.00 176.58   93
 16  \w     14.00  41.00   0.30    0.30    --   46.00  80.00-164.03   90
 17  \w     14.00  41.00   0.30    0.30    --   46.00  79.00 -10.55   90
 18  \w     14.00  41.00   0.30    0.30    --   46.00  79.00 134.39   90
 19  \w     14.00  41.00   0.30    0.30    --   46.00  80.00 170.33   90
 20  \w     14.00  41.00   0.30    0.30    --   46.00  80.00  52.25   90
 21  \w     25.00 124.00   0.30    0.30    --   54.00  69.00 -59.78  330
 22  \w     29.00 128.00   0.30    0.30    --   58.00  67.00 159.18  330
 23  \w     30.00 127.20   0.30    0.30    --   58.00  64.00  11.88  324
 24  \w     32.00 134.00   0.30    0.30    --   62.00  70.00-108.45  340
 25  \w     36.00 138.00   0.30    0.30    --   66.00  71.00  56.12  340
 26  \w     36.00 138.00   0.30    0.30    --   66.00  70.00-170.71  340
 27  \w     36.00 138.00   0.30    0.30    --   66.00  71.00  82.12  340
 28  \w     36.00 138.00   0.30    0.30    --   66.00  71.00 -48.67  340
 29  \w     42.00 141.00   0.30    0.30    --   70.00  65.00-111.24  330
 30  \w     41.00 140.00   0.30    0.30    --   70.00  69.00  17.12  330
 31  \w     52.00 148.00   0.30    0.40    --   78.00  55.00  69.33  320
 32  \w     54.00 151.20   0.30    0.40    --   82.00  63.00 -94.52  324
 33  \w     54.00 151.20   0.30    0.40    --   82.00  64.00  99.88  324
 34  \w     53.00 152.00   0.30    0.40    --   82.00  67.00 143.77  330
 35  \w     59.00 155.00   0.30    0.40    --   86.00  59.00 -53.36  320
 36  \w     59.00 155.00   0.30    0.40    --   86.00  57.00  92.63  320
 37  \w     65.00 164.00   0.30    0.40    --   94.00  67.00 143.18  330
 38  \w     64.00 166.00   0.30    0.40    --   94.00  70.00   3.35  340
 39  \w     67.00 163.00   0.30    0.40    --   94.00  58.00   0.36  320
 40  \w     66.00 163.20   0.30    0.40    --   94.00  61.00-159.94  324
 41  \w     64.00 166.00   0.30    0.40    --   94.00  71.00 -43.21  340
 42  \w     69.00 168.00   0.30    0.40    --   98.00  68.00  70.17  330
 43  \w     69.00 168.00   0.30    0.40    --   98.00  67.00-101.72  330
 44  \w     72.00 168.00   0.30    0.40    --   98.00  53.00 128.54  320
 45  \w     76.00 178.00   0.30    0.40    --  106.00  70.00  -7.47  340
 46  \w     34.00 106.90   0.30    0.40    --  111.00-105.00 157.13  243
 47  \w     84.00 177.00   0.30    0.40    --  111.00  59.00 172.11  310
 48  \w     30.00 105.90   0.30    0.40    --  111.00 -94.00-120.00  253
 49  \w     41.00 138.20   0.30    0.40    --  111.00 -61.00  90.00  324
 50  \w     40.00 134.20   0.30    0.40    --  111.00 -45.00-180.00  314
 51  \w     83.00 177.20   0.30    0.40    --  111.00  61.00 -60.00  314
 52  \w     36.00 108.00   0.30    0.40    --  111.00-111.00  30.00  240
 53  \w     83.00 177.20   0.30    0.40    --  111.00  61.00 120.00  314
 54  \w     30.00 105.90   0.30    0.40    --  111.00 -94.00  60.00  253
 55  \w     83.00 177.20   0.30    0.40    --  111.00  61.00  30.00  314
 56  \w     83.00 177.20   0.30    0.40    --  111.00  61.00  90.00  314
 57  \w     83.00 177.20   0.30    0.40    --  111.00  61.00-120.00  314
 58  \w     83.00 177.20   0.30    0.40    --  111.00  61.00-150.00  314
 59  \w     87.00 177.00   0.30    0.40    --  111.00  45.00 -90.00  300
 60  \w     87.00 177.00   0.30    0.40    --  111.00  45.00-150.00  300
 61  \w     83.00 177.20   0.30    0.40    --  111.00  64.00  59.76  314
 62  \w     30.00 105.90   0.30    0.40    --  111.00 -94.00-180.00  253
 63  \w     83.00 177.20   0.30    0.40    --  111.00  61.00 150.00  314
 64  \w     37.00 142.00   0.30    0.40    --  111.00 -77.00 -60.00  350
 65  \w     87.00 177.00   0.30    0.40    --  111.00  45.00  60.00  300
 66  \w     83.00 177.20   0.30    0.40    --  111.00  61.00 -30.00  314
 67  \w      6.00 121.20   0.30    0.30    --   43.37  19.00  90.00  384
 68  \w     13.00  40.90   0.30    0.30    --   46.00  82.00  99.72   93
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0737223000
_diffrn_orient_matrix_UB_12      -0.0544380000
_diffrn_orient_matrix_UB_13      0.1097176000
_diffrn_orient_matrix_UB_21      -0.1423046000
_diffrn_orient_matrix_UB_22      0.1381935000
_diffrn_orient_matrix_UB_23      -0.0124174000
_diffrn_orient_matrix_UB_31      -0.1232355000
_diffrn_orient_matrix_UB_32      -0.1366794000
_diffrn_orient_matrix_UB_33      -0.0122938000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0259
_diffrn_reflns_av_unetI/netI     0.0120
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            33181
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.698
_diffrn_reflns_theta_min         5.797
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.909
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.802
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.51a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'translucent light colourless'
_exptl_crystal_density_diffrn    1.427
_exptl_crystal_description       irregular
_exptl_crystal_F_000             384
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.270
_refine_diff_density_min         -0.176
_refine_diff_density_rms         0.037
_refine_ls_extinction_coef       0.0017(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     246
_refine_ls_number_reflns         3560
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0403
_refine_ls_R_factor_gt           0.0359
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0402P)^2^+0.3324P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0888
_refine_ls_wR_factor_ref         0.0923
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3216
_reflns_number_total             3560
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob00122a2.cif
_cod_data_source_block           bau32
_cod_depositor_comments
'Adding full bibliography for 7159144--7159146.cif.'
_cod_database_code               7159144
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C22 H18 O3 F2'
_chemical_oxdiff_usercomment     'Compund 4B, Bau032'
_shelx_estimated_absorpt_t_max   0.915
_shelx_estimated_absorpt_t_min   0.868
_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:
 C1(H1A,H1B), C10(H10A,H10B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B)
2.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C9(H9), C22(H22), C24(H24), C25(H25)
2.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C)
;
_shelx_res_checksum              33574
_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 1.154
_oxdiff_exptl_absorpt_empirical_full_min 0.854