Regioselective Chlorolactonization of Styrene-Type Carboxylic Esters and Amides via PhICl<sub>2</sub>-Mediated Oxidative C-O/C-Cl Bond Formations.
Xing, Linlin; Zhang, Yong; Zhang, Yilin; Ai, Zhenkang; Li, Xuemin; Du, Yunfei; Deng, Jun; Zhao, Kang; The Journal of organic chemistry 84 (2019) 13832–13840; doi:10.1021/acs.joc.9b02022

data_4034575
_publ_section_title
;
 Regioselective Chlorolactonization of Styrene-Type Carboxylic Esters and
 Amides via PhICl<sub>2</sub>-Mediated Oxidative C-O/C-Cl Bond Formations.
;
_journal_issue                   21
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              13832
_journal_page_last               13840
_journal_paper_doi               10.1021/acs.joc.9b02022
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C16 H10 Cl F3 O2'
_chemical_formula_sum            'C16 H10 Cl F3 O2'
_chemical_formula_weight         326.69
_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             2019-05-21
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                106.3018(10)
_cell_angle_beta                 101.8930(9)
_cell_angle_gamma                103.8361(10)
_cell_formula_units_Z            2
_cell_length_a                   8.30352(8)
_cell_length_b                   8.62547(11)
_cell_length_c                   10.50067(11)
_cell_measurement_reflns_used    17174
_cell_measurement_temperature    160.00(10)
_cell_measurement_theta_max      76.9870
_cell_measurement_theta_min      4.5700
_cell_volume                     670.100(15)
_computing_cell_refinement       'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_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      160.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.986
_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    -78.00  27.00   0.50    0.05    --  -46.37  94.00 143.00  210
  2  \w    -25.00  78.00   0.50    0.05    --   46.37 -94.00  32.00  206
  3  \w   -109.00 -27.00   0.50    0.10    -- -100.00  94.00 143.00  164
  4  \w   -173.00 -84.00   0.50    0.10    -- -100.00 -94.00  32.00  178
  5  \w     35.00 109.00   0.50    0.10    --  107.75 -94.00  32.00  148
  6  \w     78.00 178.00   0.50    0.10    --  107.75  94.00 143.00  200
  7  \w    -23.00   8.00   0.50    0.05    --   12.00 100.00 165.42   62
  8  \w     -9.00  17.00   0.50    0.05    --   24.00  97.00 175.20   52
  9  \w     10.00  39.00   0.50    0.05    --   40.00  90.00-176.26   58
 10  \w   -118.00 -23.00   0.50    0.05    --  -46.37 -77.00   0.00  190
 11  \w    -95.00 -20.00   0.50    0.05    --  -46.37 125.00 -30.00  150
 12  \w     32.00 120.00   0.50    0.05    --   46.37  37.00  60.00  176
 13  \w     30.00 118.00   0.50    0.05    --   46.37  57.00 -60.00  176
 14  \w     23.00 118.00   0.50    0.05    --   46.37  77.00 120.00  190
 15  \w     23.00 118.00   0.50    0.05    --   46.37  77.00 -90.00  190
 16  \w     22.00 121.00   0.50    0.05    --   48.00  83.00   3.56  198
 17  \w     23.00 121.00   0.50    0.05    --   48.00  81.00  71.86  196
 18  \w     28.00 125.00   0.50    0.05    --   52.00  78.00 170.76  194
 19  \w   -128.00 -32.00   0.50    0.05    --  -56.00 -76.00  68.49  192
 20  \w     32.00 129.00   0.50    0.05    --   56.00  78.00  35.25  194
 21  \w     33.00 129.00   0.50    0.05    --   56.00  76.00 -13.73  192
 22  \w     31.00 129.00   0.50    0.05    --   56.00  80.00 -73.74  196
 23  \w     33.00 129.00   0.50    0.05    --   56.00  76.00-148.18  192
 24  \w   -137.00 -37.00   0.50    0.05    --  -64.00 -84.00-162.67  200
 25  \w     42.00 137.00   0.50    0.05    --   64.00  73.00  40.19  190
 26  \w   -140.00 -47.00   0.50    0.05    --  -68.00 -70.00  85.77  186
 27  \w   -140.00 -49.00   0.50    0.05    --  -68.00 -66.00  33.05  182
 28  \w   -140.00 -42.00   0.50    0.05    --  -68.00 -82.00-114.40  196
 29  \w   -140.00 -48.00   0.50    0.05    --  -68.00 -68.00 103.94  184
 30  \w   -145.00 -52.00   0.50    0.05    --  -72.00 -68.00 130.70  186
 31  \w   -145.00 -45.00   0.50    0.05    --  -72.00 -84.00 100.03  200
 32  \w     48.00 145.00   0.50    0.05    --   72.00  77.00-134.73  194
 33  \w    -86.00 -50.00   0.50    0.10    --  -76.00 -81.00 -51.97   72
 34  \w    -74.00 -49.00   0.50    0.10    --  -76.00 -84.00  19.62   50
 35  \w    -92.00 -57.00   0.50    0.10    --  -80.00 -74.00-163.92   70
 36  \w   -143.00-117.00   0.50    0.10    --  -80.00 -76.00-124.60   52
 37  \w    -90.00 -58.00   0.50    0.10    --  -80.00 -73.00  34.29   64
 38  \w    -81.00 -56.00   0.50    0.10    --  -80.00 -76.00-124.60   50
 39  \w    -81.00 -55.00   0.50    0.10    --  -80.00 -81.00 -10.00   52
 40  \w   -146.00-121.00   0.50    0.10    --  -80.00 -81.00 -10.00   50
 41  \w    -96.00 -62.00   0.50    0.10    --  -84.00 -74.00 -87.01   68
 42  \w    -82.00 -57.00   0.50    0.10    --  -84.00 -84.00  99.18   50
 43  \w    -93.00 -62.00   0.50    0.10    --  -84.00 -82.00-173.49   62
 44  \w   -107.00 -69.00   0.50    0.10    --  -88.00 -72.00  15.10   76
 45  \w    -99.00 -65.00   0.50    0.10    --  -88.00 -74.00 -22.46   68
 46  \w    -99.00 -71.00   0.50    0.10    --  -92.00 -69.00 121.59   56
 47  \w    -98.00 -68.00   0.50    0.10    --  -92.00 -77.00  38.31   60
 48  \w   -107.00 -73.00   0.50    0.10    --  -92.00 -66.00-116.33   68
 49  \w   -105.00 -80.00   0.50    0.10    --  -96.00 -61.00 156.53   50
 50  \w   -169.00-138.00   0.50    0.10    --  -96.00 -61.00 156.53   62
 51  \w   -104.00 -76.00   0.50    0.10    -- -100.00 -76.00 -36.54   56
 52  \w   -111.00 -76.00   0.50    0.10    -- -100.00 -77.00 -56.25   70
 53  \w   -124.00 -76.00   0.50    0.10    -- -100.00 -77.00 150.00   96
 54  \w   -106.00 -80.00   0.50    0.10    -- -100.00 -77.00   0.00   52
 55  \w   -164.00-138.00   0.50    0.10    -- -100.00 -77.00   0.00   52
 56  \w   -109.00 -79.00   0.50    0.10    -- -100.00 -70.00  45.10   60
 57  \w   -102.00 -76.00   0.50    0.10    -- -100.00 -78.00 127.17   52
 58  \w   -105.00 -77.00   0.50    0.10    -- -100.00 -77.00   6.99   56
 59  \w   -104.00 -77.00   0.50    0.10    -- -100.00 -77.00-120.00   54
 60  \w   -112.00 -76.00   0.50    0.10    -- -100.00 -77.00-150.00   72
 61  \w   -166.00-130.00   0.50    0.10    -- -100.00 -77.00-150.00   72
 62  \w   -124.00 -81.00   0.50    0.10    -- -100.00 -66.00-122.25   86
 63  \w   -109.00 -73.00   0.50    0.10    -- -100.00 -84.00  86.10   72
 64  \w   -164.00-138.00   0.50    0.10    -- -100.00 -84.00  86.10   52
 65  \w   -102.00 -75.00   0.50    0.10    -- -100.00 -80.00 115.51   54
 66  \w     76.00 120.00   0.50    0.10    --  107.75 -30.00   0.00   88
 67  \w     33.00  69.00   0.50    0.10    --  107.75 -30.00   0.00   72
 68  \w     78.00 106.00   0.50    0.10    --  107.75 -94.00 -30.00   56
 69  \w     35.00  76.00   0.50    0.10    --  107.75 -94.00 -30.00   82
 70  \w    149.00 175.00   0.50    0.10    --  107.75  77.00  90.00   52
 71  \w    105.00 132.00   0.50    0.10    --  107.75 -77.00  90.00   54
 72  \w     86.00 132.00   0.50    0.10    --  107.75  77.00  90.00   92
 73  \w    136.00 178.00   0.50    0.10    --  107.75  77.00  60.00   84
 74  \w     62.00  91.00   0.50    0.10    --  107.75 -77.00  90.00   58
 75  \w     41.00 108.00   0.50    0.10    --  107.75 -94.00-150.00  134
 76  \w     86.00 123.00   0.50    0.10    --  107.75  77.00  60.00   74
 77  \w     90.00 116.00   0.50    0.10    --  107.75-125.00 -60.00   52
 78  \w     97.00 178.00   0.50    0.10    --  107.75  45.00-150.00  162
 79  \w     84.00 118.00   0.50    0.10    --  107.75  77.00  30.00   68
 80  \w    124.00 150.00   0.50    0.10    --  107.75  45.00-120.00   52
 81  \w     39.00 108.00   0.50    0.10    --  107.75 -94.00 150.00  138
 82  \w     79.00 104.00   0.50    0.10    --  107.75 -94.00  60.00   50
 83  \w    145.00 172.00   0.50    0.10    --  107.75 125.00 -60.00   54
 84  \w     74.00 100.00   0.50    0.10    --  107.75 125.00 -60.00   52
 85  \w     80.00 108.00   0.50    0.10    --  107.75 -94.00 -60.00   56
 86  \w     78.00 117.00   0.50    0.10    --  107.75-125.00 120.00   78
 87  \w     35.00  72.00   0.50    0.10    --  107.75-125.00 120.00   74
 88  \w     40.00  70.00   0.50    0.10    --  107.75 -94.00 -60.00   60
 89  \w     85.00 123.00   0.50    0.10    --  107.75  77.00 -30.00   76
 90  \w     86.00 169.00   0.50    0.10    --  107.75  77.00 -60.00  166
 91  \w    143.00 176.00   0.50    0.10    --  107.75  77.00 150.00   66
 92  \w     87.00 127.00   0.50    0.10    --  107.75  77.00 150.00   80
 93  \w     86.00 161.00   0.50    0.10    --  107.75  77.00   0.00  150
 94  \w    119.00 145.00   0.50    0.10    --  107.75  61.00 120.00   52
 95  \w     37.00  92.00   0.50    0.10    --  107.75-125.00  30.00  110
 96  \w     90.00 141.00   0.50    0.10    --  107.75  61.00-150.00  102
 97  \w     69.00 114.00   0.50    0.10    --  107.75 -15.00 150.00   90
 98  \w     36.00  63.00   0.50    0.10    --  107.75 -15.00 150.00   54
 99  \w     68.00 107.00   0.50    0.10    --  107.75 -45.00   0.00   78
100  \w    129.00 166.00   0.50    0.10    --  107.75  77.00  30.00   74
101  \w    133.00 173.00   0.50    0.10    --  107.75  77.00 120.00   80
102  \w     84.00 127.00   0.50    0.10    --  107.75  77.00 120.00   86
103  \w    130.00 178.00   0.50    0.10    --  107.75  61.00 -90.00   96
104  \w     97.00 178.00   0.50    0.10    --  107.75  30.00  90.00  162
105  \w     90.00 127.00   0.50    0.10    --  107.75  61.00 -90.00   74
106  \w     92.00 134.00   0.50    0.10    --  107.75  77.00 -90.00   84
107  \w     92.00 167.00   0.50    0.10    --  107.75  61.00 -30.00  150
108  \w     36.00  98.00   0.50    0.10    --  107.75 -61.00-150.00  124
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1853063000
_diffrn_orient_matrix_UB_12      0.0050391000
_diffrn_orient_matrix_UB_13      -0.0047879000
_diffrn_orient_matrix_UB_21      -0.0690524000
_diffrn_orient_matrix_UB_22      -0.1325379000
_diffrn_orient_matrix_UB_23      -0.1480267000
_diffrn_orient_matrix_UB_31      -0.0289134000
_diffrn_orient_matrix_UB_32      -0.1445141000
_diffrn_orient_matrix_UB_33      0.0602253000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0380
_diffrn_reflns_av_unetI/netI     0.0158
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            26594
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.205
_diffrn_reflns_theta_min         4.589
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.921
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80390
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.45g (Rigaku Oxford Diffraction, 2018)
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    1.619
_exptl_crystal_description       block
_exptl_crystal_F_000             332
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.280
_refine_diff_density_min         -0.258
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.080
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     199
_refine_ls_number_reflns         2805
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.0298
_refine_ls_R_factor_gt           0.0282
_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^)+(0.0388P)^2^+0.2738P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0752
_refine_ls_wR_factor_ref         0.0778
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2677
_reflns_number_total             2805
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02022_si_001.cif
_cod_data_source_block           dyf-3
_cod_original_cell_volume        670.100(14)
_cod_database_code               4034575
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.759
_shelx_estimated_absorpt_t_min   0.759
_reflns_odcompleteness_completeness 99.74
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7), C8(H8)
2.b Aromatic/amide H refined with riding coordinates:
 C13(H13), C15(H15), C12(H12), C1(H1), C5(H5), C4(H4), C3(H3), C2(H2)
;
_shelx_res_checksum              54124
_shelx_hkl_checksum              26917
_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 2.279
_oxdiff_exptl_absorpt_empirical_full_min 0.653