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_1566901
_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         'C23 H18 Cl F3 O3'
_chemical_formula_sum            'C23 H18 Cl F3 O3'
_chemical_formula_weight         434.82
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2021-08-19
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-09-08 deposited with the CCDC.	2022-05-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.018(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.5234(6)
_cell_length_b                   9.7432(5)
_cell_length_c                   17.5168(9)
_cell_measurement_reflns_used    8012
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      59.5840
_cell_measurement_theta_min      4.5020
_cell_volume                     2121.35(19)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_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     78.00 103.00   0.50    0.05    --   73.53  58.00  61.00   50
  2  \w     21.00  47.00   0.50    0.05    --   73.53 -58.00 -79.00   52
  3  \w     32.00  70.00   0.50    0.05    --   73.53 -38.00-180.00   76
  4  \w    -14.00  21.00   0.50    0.05    --   -0.62  38.00-180.00   70
  5  \w     26.00  60.00   0.50    0.05    --   -0.62  38.00-180.00   68
  6  \w    -17.00  70.00   0.50    0.05    --   -0.62  58.00  61.00  174
  7  \w    -89.00  -5.00   0.50    0.05    --  -74.78  58.00  61.00  168
  8  \w    -67.00 -15.00   0.50    0.05    --  -74.78  38.00  30.00  104
  9  \w    -56.00 -28.00   0.50    0.05    --   -0.62 -58.00 -79.00   56
 10  \w   -142.00 -91.00   0.50    0.05    --  -74.78 -99.00  60.00  102
 11  \w   -146.00 -80.00   0.50    0.05    --  -74.78-125.00  60.00  132
 12  \w   -146.00 -87.00   0.50    0.05    --  -74.78-125.00   0.00  118
 13  \w   -144.00-110.00   0.50    0.05    --  -74.78 -99.00  30.00   68
 14  \w   -148.00 -80.00   0.50    0.05    --  -74.78 -58.00 -79.00  136
 15  \w   -147.00 -96.00   0.50    0.05    --  -74.78 -99.00-180.00  102
;
_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      -0.0572864000
_diffrn_orient_matrix_UB_12      0.0933904000
_diffrn_orient_matrix_UB_13      -0.0436252000
_diffrn_orient_matrix_UB_21      0.0668518000
_diffrn_orient_matrix_UB_22      -0.0131294000
_diffrn_orient_matrix_UB_23      -0.0536671000
_diffrn_orient_matrix_UB_31      -0.0620427000
_diffrn_orient_matrix_UB_32      -0.1001881000
_diffrn_orient_matrix_UB_33      -0.0338151000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Ga K\a'
_diffrn_radiation_wavelength     1.3405
_diffrn_reflns_av_R_equivalents  0.0286
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            15318
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        53.543
_diffrn_reflns_theta_max         60.778
_diffrn_reflns_theta_min         4.523
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    1.324
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57361
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.361
_exptl_crystal_description       irregular
_exptl_crystal_F_000             896
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.022
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.446
_refine_diff_density_min         -0.586
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.123
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     273
_refine_ls_number_reflns         4752
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.123
_refine_ls_R_factor_all          0.0786
_refine_ls_R_factor_gt           0.0626
_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^)+(0.1014P)^2^+0.3792P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1826
_refine_ls_wR_factor_ref         0.1974
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3479
_reflns_number_total             4752
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00902a3.cif
_cod_data_source_block           zq-6-58-2_auto
_cod_database_code               1566901
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHOClF
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.961
_reflns_odcompleteness_completeness 99.63
_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:
 C00B(H00C)
2.b Secondary CH2 refined with riding coordinates:
 C009(H00A,H00B), C00J(H00D,H00E)
2.c Aromatic/amide H refined with riding coordinates:
 C00H(H00H), C00K(H00K), C00P(H00P), C00Q(H00Q), C00R(H00R), C00S(H00S),
 C00U(H00U)
2.d Idealised Me refined as rotating group:
 C00L(H00F,H00G,H00I), C00T(H00J,H00L,H00M)
;
_shelx_res_checksum              86515
_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 1.828
_oxdiff_exptl_absorpt_empirical_full_min 0.687