Simple generation of various α-monofluoroalkyl radicals by organic photoredox catalysis: modular synthesis of β-monofluoroketones.
Taniguchi, Ryo; Noto, Naoki; Tanaka, Seiya; Takahashi, Keigo; Sarkar, Sujan K.; Oyama, Ryoko; Abe, Manabu; Koike, Takashi; Akita, Munetaka; Chemical communications (Cambridge, England) 57 (2021) 2609–2612; doi:10.1039/d0cc08060h

data_7127952
_publ_section_title
;
 Simple generation of various \a-monofluoroalkyl radicals by organic
 photoredox catalysis: modular synthesis of \b-monofluoroketones.
;
_journal_issue                   21
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              2609
_journal_page_last               2612
_journal_paper_doi               10.1039/d0cc08060h
_journal_volume                  57
_journal_year                    2021
_chemical_formula_moiety         'C21 H20 F N O3 S2'
_chemical_formula_sum            'C21 H20 F N O3 S2'
_chemical_formula_weight         417.50
_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
_audit_creation_date             2020-05-29
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-11-30 deposited with the CCDC.	2021-02-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.416(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.1286(7)
_cell_length_b                   5.7699(2)
_cell_length_c                   15.7586(5)
_cell_measurement_reflns_used    27113
_cell_measurement_temperature    93
_cell_measurement_theta_max      76.3960
_cell_measurement_theta_min      4.2030
_cell_volume                     1930.03(11)
_computing_cell_refinement       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_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      93.0
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.969
_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     92.00 177.00   0.50    0.40    --  104.61  24.00 108.00  170
  2  \w     35.00 112.00   0.50    0.10    --   46.57  24.00 108.00  154
  3  \w     32.00  64.00   0.50    0.40    --  104.61 -61.00 120.00   64
  4  \w    -16.00  44.00   0.50    0.10    --   46.57 -37.00 150.00  120
  5  \w     33.00  72.00   0.50    0.40    --  104.61 -61.00   0.00   78
  6  \w    110.00 162.00   0.50    0.40    --  104.61  45.00-150.00  104
  7  \w    -15.00  11.00   0.50    0.10    --   46.57 -24.00 -56.00   52
  8  \w     52.00  99.00   0.50    0.40    --  104.61 -94.00-120.00   94
  9  \w     34.00  76.00   0.50    0.40    --  104.61 -94.00 -90.00   84
 10  \w    -24.00   1.00   0.50    0.10    --  -46.57  24.00 108.00   50
 11  \w    -98.00 -72.00   0.50    0.40    -- -102.00  77.00   0.00   52
 12  \w    -64.00 -29.00   0.50    0.40    -- -102.00  61.00  90.00   70
 13  \w    -67.00 -29.00   0.50    0.40    -- -102.00  61.00  60.00   76
 14  \w    -56.00 -29.00   0.50    0.40    -- -102.00  61.00  30.00   54
 15  \w    -64.00 -32.00   0.50    0.40    -- -102.00  77.00   0.00   64
 16  \w    -69.00 -43.00   0.50    0.40    -- -102.00  61.00   0.00   52
 17  \w    -68.00 -41.00   0.50    0.40    -- -102.00  61.00 -90.00   54
 18  \w    -65.00 -29.00   0.50    0.40    -- -102.00  61.00 -60.00   72
 19  \w    -65.00 -35.00   0.50    0.40    -- -102.00  61.00-120.00   60
 20  \w    -69.00 -30.00   0.50    0.40    -- -102.00  61.00-150.00   78
 21  \w    -69.00 -44.00   0.50    0.40    -- -102.00  61.00-180.00   50
 22  \w   -103.00 -40.00   0.50    0.10    --  -46.57 -24.00 -56.00  126
 23  \w   -133.00 -89.00   0.50    0.40    -- -102.00 -24.00 -56.00   88
 24  \w   -115.00 -86.00   0.50    0.10    --  -46.57-125.00  30.00   58
 25  \w    -63.00 -37.00   0.50    0.10    --  -46.57 -41.00 160.63   52
 26  \w    -91.00 -35.00   0.50    0.10    --  -46.57 -37.00-150.00  112
 27  \w    -72.00 -34.00   0.50    0.10    --  -46.57 -46.00 -29.00   76
 28  \w    -76.00 -35.00   0.50    0.10    --  -46.57 -43.00  66.99   82
 29  \w     24.00  53.00   0.50    0.10    --   46.57  77.00 120.00   58
 30  \w     89.00 115.00   0.50    0.10    --   46.57  77.00-180.00   52
 31  \w     26.00  61.00   0.50    0.10    --   46.57  77.00   0.00   70
 32  \w     37.00 115.00   0.50    0.10    --   46.57  37.00-180.00  156
 33  \w     25.00  52.00   0.50    0.10    --   46.57  77.00  30.00   54
 34  \w     24.00  56.00   0.50    0.10    --   46.57  77.00 -60.00   64
 35  \w     25.00  60.00   0.50    0.10    --   46.57  77.00 150.00   70
 36  \w     22.00  86.00   0.50    0.10    --   46.57-125.00  30.00  128
 37  \w     24.00  59.00   0.50    0.10    --   46.57  77.00 -30.00   70
 38  \w     25.00  66.00   0.50    0.10    --   46.57  77.00-180.00   82
 39  \w     33.00  61.00   0.50    0.10    --   46.57  57.00-120.00   56
 40  \w     24.00 103.00   0.50    0.10    --   46.57  77.00-120.00  158
 41  \w     33.00  58.00   0.50    0.10    --   46.57  57.00   0.00   50
 42  \w     18.00  88.00   0.50    0.10    --   46.57-125.00-150.00  140
 43  \w     24.00  64.00   0.50    0.10    --   46.57  77.00  60.00   80
 44  \w   -173.00 -86.00   0.50    0.40    -- -102.00 -59.00  60.07  174
 45  \w   -170.00-144.00   0.50    0.40    -- -102.00 -72.00   0.93   52
 46  \w   -104.00 -79.00   0.50    0.40    -- -102.00 -78.00  39.60   50
 47  \w   -105.00 -79.00   0.50    0.40    -- -102.00 -76.00-109.89   52
 48  \w   -173.00-147.00   0.50    0.40    -- -102.00 -78.00  39.60   52
 49  \w   -107.00 -81.00   0.50    0.40    -- -102.00 -72.00 135.96   52
 50  \w   -106.00 -79.00   0.50    0.40    -- -102.00 -79.00 -97.06   54
 51  \w   -106.00 -80.00   0.50    0.40    -- -102.00 -74.00 -34.11   52
 52  \w   -107.00 -81.00   0.50    0.40    -- -102.00 -72.00   0.93   52
 53  \w   -174.00-148.00   0.50    0.40    -- -102.00 -62.00 -39.80   52
 54  \w   -162.00 -85.00   0.50    0.40    -- -102.00 -61.00 -90.00  154
 55  \w   -107.00 -81.00   0.50    0.40    -- -102.00 -72.00 108.98   52
 56  \w   -105.00 -79.00   0.50    0.40    -- -102.00 -77.00  72.46   52
 57  \w   -122.00 -88.00   0.50    0.40    -- -102.00 -50.00  -9.04   68
 58  \w   -118.00 -85.00   0.50    0.40    -- -102.00 -61.00-150.00   66
 59  \w   -170.00-136.00   0.50    0.40    -- -102.00 -72.00 108.98   68
 60  \w   -110.00 -84.00   0.50    0.40    -- -102.00 -64.00 139.42   52
 61  \w   -104.00 -78.00   0.50    0.40    -- -102.00 -80.00  58.48   52
 62  \w   -108.00 -81.00   0.50    0.40    -- -102.00 -72.00 160.30   54
 63  \w   -133.00 -83.00   0.50    0.40    -- -102.00 -67.00 161.50  100
 64  \w   -167.00-140.00   0.50    0.40    -- -102.00 -80.00  58.48   54
 65  \w   -105.00 -80.00   0.50    0.40    -- -102.00 -75.00 -98.01   50
 66  \w   -104.00 -78.00   0.50    0.40    -- -102.00 -80.00 130.41   52
 67  \w   -162.00-137.00   0.50    0.40    -- -102.00 -80.00 130.41   50
 68  \w   -130.00 -79.00   0.50    0.40    -- -102.00 -77.00 -60.00  102
 69  \w   -113.00 -86.00   0.50    0.40    -- -102.00 -61.00  90.00   54
 70  \w   -167.00-129.00   0.50    0.40    -- -102.00 -74.00 -13.78   76
 71  \w   -108.00 -80.00   0.50    0.40    -- -102.00 -74.00 -13.78   56
 72  \w   -111.00 -79.00   0.50    0.40    -- -102.00 -77.00-180.00   64
 73  \w   -156.00-129.00   0.50    0.40    -- -102.00 -77.00  90.00   54
 74  \w   -104.00 -79.00   0.50    0.40    -- -102.00 -77.00  90.00   50
 75  \w   -159.00 -85.00   0.50    0.40    -- -102.00 -61.00-180.00  148
 76  \w   -166.00 -85.00   0.50    0.40    -- -102.00 -61.00 -60.00  162
 77  \w   -111.00 -79.00   0.50    0.40    -- -102.00 -77.00-120.00   64
 78  \w   -107.00 -80.00   0.50    0.40    -- -102.00 -74.00-155.71   54
 79  \w   -133.00 -87.00   0.50    0.40    -- -102.00 -55.00-107.27   92
 80  \w   -171.00-145.00   0.50    0.40    -- -102.00 -74.00-155.71   52
 81  \w   -166.00-141.00   0.50    0.40    -- -102.00 -75.00 -98.01   50
 82  \w   -110.00 -85.00   0.50    0.40    -- -102.00 -61.00   0.00   50
 83  \w   -172.00 -85.00   0.50    0.40    -- -102.00 -61.00  30.00  174
 84  \w   -136.00 -79.00   0.50    0.40    -- -102.00 -77.00  60.00  114
 85  \w   -105.00 -79.00   0.50    0.40    -- -102.00 -76.00-172.12   52
 86  \w   -105.00 -79.00   0.50    0.40    -- -102.00 -77.00  30.00   52
 87  \w   -105.00 -79.00   0.50    0.40    -- -102.00 -77.00 -90.00   52
 88  \w   -110.00 -85.00   0.50    0.40    -- -102.00 -62.00 -39.80   50
 89  \w   -105.00 -79.00   0.50    0.40    -- -102.00 -77.00-150.00   52
 90  \w   -136.00-110.00   0.50    0.40    -- -102.00 -77.00-150.00   52
 91  \w   -172.00-146.00   0.50    0.40    -- -102.00 -55.00-107.27   52
 92  \w   -105.00 -79.00   0.50    0.40    -- -102.00 -77.00   0.00   52
 93  \w   -152.00 -89.00   0.50    0.40    -- -102.00 -45.00-180.00  126
 94  \w     33.00 104.00   0.50    0.40    --  104.61 -94.00  90.00  142
 95  \w     78.00 104.00   0.50    0.40    --  104.61 -94.00   0.00   52
 96  \w     33.00 104.00   0.50    0.40    --  104.61 -94.00 -60.00  142
 97  \w     70.00 105.00   0.50    0.40    --  104.61 -77.00 -60.00   70
 98  \w     34.00  60.00   0.50    0.40    --  104.61 -77.00 -60.00   52
 99  \w     79.00 105.00   0.50    0.40    --  104.61 -77.00  90.00   52
100  \w     44.00  70.00   0.50    0.40    --  104.61 -77.00  90.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0695707000
_diffrn_orient_matrix_UB_12      -0.0742938000
_diffrn_orient_matrix_UB_13      0.0332905000
_diffrn_orient_matrix_UB_21      0.0015111000
_diffrn_orient_matrix_UB_22      -0.0360669000
_diffrn_orient_matrix_UB_23      -0.0962979000
_diffrn_orient_matrix_UB_31      0.0206691000
_diffrn_orient_matrix_UB_32      0.2536749000
_diffrn_orient_matrix_UB_33      -0.0039393000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0528
_diffrn_reflns_av_unetI/netI     0.0200
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            48671
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.274
_diffrn_reflns_theta_min         4.165
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.782
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81272
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.68a (Rigaku Oxford Diffraction, 2019)
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    1.437
_exptl_crystal_description       prism
_exptl_crystal_F_000             872
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetone/MeOH'
_exptl_crystal_size_max          0.268
_exptl_crystal_size_mid          0.065
_exptl_crystal_size_min          0.054
_refine_diff_density_max         0.483
_refine_diff_density_min         -0.341
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     254
_refine_ls_number_reflns         3925
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0363
_refine_ls_R_factor_gt           0.0347
_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^)+(0.0532P)^2^+1.1604P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0953
_refine_ls_wR_factor_ref         0.0966
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3719
_reflns_number_total             3925
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc08060h2.cif
_cod_data_source_block           rt277
_cod_depositor_comments
'Adding full bibliography for 7127952--7127955.cif.'
_cod_database_code               7127952
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C21H20FNO3S2
_shelx_estimated_absorpt_t_max   0.864
_shelx_estimated_absorpt_t_min   0.523
_diffrn_oxdiff_digest_frames
;
01be8a550bd2ed6ca7c72ae836e397e2540004186e9
;
_diffrn_oxdiff_digest_hkl
;
013705b80824340b0b48519d092adfde72a0b0
;
_reflns_odcompleteness_completeness 99.92
_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.a Ternary CH refined with riding coordinates:
 C1(H1)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B)
2.c Aromatic/amide H refined with riding coordinates:
 C20(H20), C14(H14), C19(H19), C10(H10), C17(H17), C13(H13), C16(H16),
 C11(H11), C12(H12), C4(H4), C5(H5), C8(H8), C6(H6), C7(H7)
2.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C)
;
_shelx_res_checksum              80490
_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 1.413
_oxdiff_exptl_absorpt_empirical_full_min 0.601