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_1566902
_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 H19 F3 O3'
_chemical_formula_sum            'C22 H19 F3 O3'
_chemical_formula_weight         388.37
_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             2021-08-18
_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                 111.112(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.1282(19)
_cell_length_b                   11.8989(10)
_cell_length_c                   11.6230(15)
_cell_measurement_reflns_used    4254
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      54.4320
_cell_measurement_theta_min      4.2090
_cell_volume                     1951.8(4)
_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 0.995
_diffrn_measured_fraction_theta_max 0.958
_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     63.00  97.00   0.50    0.80    --   72.28  57.00 150.00   68
  2  \w    119.00 144.00   0.50    0.80    --   72.28  57.00 150.00   50
  3  \w     77.00 102.00   0.50    0.80    --   72.28  45.00  21.00   50
  4  \w     83.00 108.00   0.50    0.80    --   72.28 125.00 -90.00   50
  5  \w     90.00 144.00   0.50    0.80    --   72.28 125.00-150.00  108
  6  \w    -31.00  -2.00   0.50    0.80    --  -74.78  38.00-150.00   58
  7  \w    -70.00  -3.00   0.50    0.80    --  -74.78  45.00  21.00  134
  8  \w    -15.00  54.00   0.50    0.20    --   -1.25  45.00  21.00  138
  9  \w     35.00  70.00   0.50    0.80    --   72.28 -45.00-128.00   70
 10  \w    -14.00  70.00   0.50    0.20    --   -1.25  57.00-180.00  168
 11  \w    -71.00 -35.00   0.50    0.80    --  -74.78  38.00-150.00   72
 12  \w   -147.00 -60.00   0.50    0.80    --  -74.78 -45.00-128.00  174
 13  \w    -72.00 -21.00   0.50    0.20    --   -1.25 -45.00-128.00  102
 14  \w    -81.00 -54.00   0.50    0.80    --  -74.78 -77.00 150.00   54
 15  \w   -148.00 -91.00   0.50    0.80    --  -74.78 -77.00 150.00  114
 16  \w   -148.00-100.00   0.50    0.80    --  -74.78-125.00 -30.00   96
 17  \w   -147.00-105.00   0.50    0.80    --  -74.78-125.00 -90.00   84
;
_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      -0.0873691000
_diffrn_orient_matrix_UB_12      0.0382456000
_diffrn_orient_matrix_UB_13      -0.0190737000
_diffrn_orient_matrix_UB_21      -0.0320994000
_diffrn_orient_matrix_UB_22      -0.0511666000
_diffrn_orient_matrix_UB_23      -0.1099759000
_diffrn_orient_matrix_UB_31      -0.0182307000
_diffrn_orient_matrix_UB_32      -0.0927611000
_diffrn_orient_matrix_UB_33      0.0529258000
_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  0.0438
_diffrn_reflns_av_unetI/netI     0.0445
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            13341
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        53.543
_diffrn_reflns_theta_max         60.697
_diffrn_reflns_theta_min         4.225
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    0.574
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.33804
_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 brownish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.322
_exptl_crystal_description       block
_exptl_crystal_F_000             808
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.521
_refine_diff_density_min         -0.290
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     254
_refine_ls_number_reflns         4310
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0966
_refine_ls_R_factor_gt           0.0647
_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^)+(0.1044P)^2^+0.3682P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1926
_refine_ls_wR_factor_ref         0.2132
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2744
_reflns_number_total             4310
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00902a3.cif
_cod_data_source_block           zq-ys_auto
_cod_database_code               1566902
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHOF
_shelx_estimated_absorpt_t_max   0.994
_shelx_estimated_absorpt_t_min   0.983
_reflns_odcompleteness_completeness 99.17
_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:
 C008(H008)
2.b Secondary CH2 refined with riding coordinates:
 C00D(H00A,H00B), C00G(H00D,H00E)
2.c Aromatic/amide H refined with riding coordinates:
 C00C(H00C), C00F(H00F), C00I(H00I), C00J(H00J), C00K(H00K), C00L(H00L),
 C00N(H00N), C00O(H00O), C00Q(H00Q), C00R(H00R), C00S(H00S)
2.d Idealised Me refined as rotating group:
 C00M(H00G,H00H,H00M)
;
_shelx_res_checksum              57588
_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 8.094
_oxdiff_exptl_absorpt_empirical_full_min 0.560