Radical 1,2,3-Tricarbofunctionalization of α-Vinyl-β-Ketoesters Enabled by Carbon Shift from All-carbon Quaternary Center
Zhang, Qi; Chiou, Mong-Feng; Ye, Changqing; Yuan, Xiaobin; Li, Yajun; Bao, Hongli; Chemical Science  (2022) –; doi:10.1039/D2SC00902A

data_1566899
_publ_section_title
;
 Radical 1,2,3-Tricarbofunctionalization of \a-Vinyl-\b-Ketoesters Enabled
 by Carbon Shift from All-carbon Quaternary Center
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC00902A
_journal_year                    2022
_chemical_formula_moiety         'C22 H17 F3 O3'
_chemical_formula_sum            'C22 H17 F3 O3'
_chemical_formula_weight         386.35
_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             2020-09-04
_audit_creation_method
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_audit_update_record
;
2021-09-08 deposited with the CCDC.	2022-05-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.403(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.6118(11)
_cell_length_b                   9.7486(8)
_cell_length_c                   17.4474(16)
_cell_measurement_reflns_used    13440
_cell_measurement_temperature    290.00(14)
_cell_measurement_theta_max      60.5890
_cell_measurement_theta_min      4.5290
_cell_volume                     1928.9(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      290.00(14)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.963
_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     61.00  87.00   0.50    0.20    --   72.03  57.00   0.00   52
  2  \w     96.00 139.00   0.50    0.20    --   72.03  57.00   0.00   86
  3  \w     81.00 143.00   0.50    0.20    --   72.03 125.00  90.00  124
  4  \w     91.00 121.00   0.50    0.20    --   72.03  93.00  75.00   60
  5  \w     49.00 103.00   0.50    0.20    --   72.03 -93.00 -36.00  108
  6  \w     21.00 106.00   0.50    0.20    --   72.03-125.00 -60.00  170
  7  \w     27.00  53.00   0.50    0.20    --   72.03-125.00-180.00   52
  8  \w     56.00  86.00   0.50    0.20    --   72.03-125.00-180.00   60
  9  \w     21.00  47.00   0.50    0.20    --   72.03 -93.00 -36.00   52
 10  \w     30.00  94.00   0.50    0.20    --   72.03 -77.00  30.00  128
 11  \w      0.00  43.00   0.50    0.20    --   72.03 -38.00 120.00   86
 12  \w     -3.00  22.00   0.50    0.20    --   72.03 -19.00 120.00   50
 13  \w     -3.00  26.00   0.50    0.20    --   72.03 -19.00  30.00   58
 14  \w     -3.00  25.00   0.50    0.20    --   72.03 -19.00   0.00   56
 15  \w     -2.00  26.00   0.50    0.20    --   72.03 -19.00 -30.00   56
 16  \w     -3.00  26.00   0.50    0.20    --   72.03 -19.00-120.00   58
 17  \w    -11.00  15.00   0.50    0.05    --   -1.72 -57.00-150.00   52
 18  \w    -29.00  11.00   0.50    0.05    --   -1.72 -93.00 -36.00   80
 19  \w    -69.00 -43.00   0.50    0.05    --   -1.72 -57.00-150.00   52
 20  \w   -112.00 -85.00   0.50    0.20    --  -75.46 -93.00 -36.00   54
 21  \w    -26.00  -1.00   0.50    0.20    --  -75.46  19.00 -90.00   50
 22  \w    -66.00 -16.00   0.50    0.20    --  -75.46  57.00-180.00  100
 23  \w    -98.00 -30.00   0.50    0.20    --  -75.46  77.00-150.00  136
 24  \w    -30.00  -5.00   0.50    0.20    --  -75.46  38.00 -90.00   50
 25  \w    -52.00  -7.00   0.50    0.20    --  -75.46  57.00 -60.00   90
 26  \w    -62.00  -7.00   0.50    0.20    --  -75.46  57.00   0.00  110
 27  \w    -42.00  -6.00   0.50    0.20    --  -75.46  38.00  60.00   72
 28  \w    -43.00  -5.00   0.50    0.20    --  -75.46  38.00 120.00   76
 29  \w     40.00  71.00   0.50    0.05    --   -1.72  57.00 -30.00   62
 30  \w    -12.00  22.00   0.50    0.05    --   -1.72  57.00 -30.00   68
 31  \w    -25.00   0.00   0.50    0.20    --  -75.46  19.00-150.00   50
 32  \w    -26.00  -1.00   0.50    0.20    --  -75.46  19.00-180.00   50
 33  \w   -106.00 -23.00   0.50    0.20    --  -75.46 125.00-180.00  166
 34  \w   -109.00 -23.00   0.50    0.20    --  -75.46 125.00   0.00  172
 35  \w    -42.00 -15.00   0.50    0.20    --  -75.46  93.00  75.00   54
 36  \w    -72.00 -46.00   0.50    0.20    --  -75.46  93.00  75.00   52
 37  \w    -32.00  30.00   0.50    0.05    --   -1.72  93.00  75.00  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      0.0328709000
_diffrn_orient_matrix_UB_12      -0.0664310000
_diffrn_orient_matrix_UB_13      0.0683808000
_diffrn_orient_matrix_UB_21      -0.0915393000
_diffrn_orient_matrix_UB_22      0.0545625000
_diffrn_orient_matrix_UB_23      0.0245799000
_diffrn_orient_matrix_UB_31      -0.0670013000
_diffrn_orient_matrix_UB_32      -0.1071946000
_diffrn_orient_matrix_UB_33      -0.0298906000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.3405
_diffrn_reflns_av_R_equivalents  0.0395
_diffrn_reflns_av_unetI/netI     0.0222
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            28814
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        53.543
_diffrn_reflns_theta_max         61.591
_diffrn_reflns_theta_min         4.512
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    0.583
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81513
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.330
_exptl_crystal_description       block
_exptl_crystal_F_000             800
_refine_diff_density_max         0.300
_refine_diff_density_min         -0.269
_refine_diff_density_rms         0.037
_refine_ls_extinction_coef       0.0033(8)
_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   1.129
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     255
_refine_ls_number_reflns         4396
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.129
_refine_ls_R_factor_all          0.0730
_refine_ls_R_factor_gt           0.0554
_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^)+(0.0759P)^2^+0.4678P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1530
_refine_ls_wR_factor_ref         0.1733
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3265
_reflns_number_total             4396
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00902a3.cif
_cod_data_source_block           zq-5-120
_cod_database_code               1566899
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHNO
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     56.82
_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:
 C2(H2)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C14(H14A,H14B)
2.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C6(H6), C8(H8), C25(H25), C7(H7), C23(H23), C26(H26), C27(H27),
 C28(H28)
2.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C)
;
_shelx_res_checksum              15835
_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 1.932
_oxdiff_exptl_absorpt_empirical_full_min 0.645