Catalyst- and additive-free cascade radical addition/cyclization of N-arylacrylamides with trifluoropyruvates
Tan, Yongbo; Huang, Huawen; Chemical Communications  (2023) –; doi:10.1039/D3CC04542K

data_7132222
_publ_section_title
;
 Catalyst- and additive-free cascade radical addition/cyclization of
 N-arylacrylamides with trifluoropyruvates
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC04542K
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H20 F3 N O4'
_chemical_formula_sum            'C21 H20 F3 N O4'
_chemical_formula_weight         407.38
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2023-06-12
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2023-06-22 deposited with the CCDC.	2023-10-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 111.190(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.2540(3)
_cell_length_b                   13.3169(2)
_cell_length_c                   19.1647(4)
_cell_measurement_reflns_used    11448
_cell_measurement_temperature    297.47(10)
_cell_measurement_theta_max      75.4810
_cell_measurement_theta_min      2.4610
_cell_volume                     4105.74(14)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      297.47(10)
_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 0.939
_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     39.00 105.12   0.38    1.00    --  109.23 -77.00-120.00  174
  2  \w     47.00  99.06   0.38    1.00    --  109.23 -77.00  30.00  137
  3  \w     37.00  65.12   0.38    1.00    --  109.23 -61.00  60.00   74
  4  \w     41.00  67.22   0.38    1.00    --  109.23 -61.00  90.00   69
  5  \w     36.00  66.78   0.38    1.00    --  109.23 -61.00 150.00   81
  6  \w    115.00 140.46   0.38    1.00    --  109.23  88.00 144.00   67
  7  \w    -76.00  27.36   0.38    0.48    --  -43.70  88.00 144.00  272
  8  \w   -121.00 -93.64   0.38    1.00    --  -96.00  88.00 144.00   72
  9  \w    -80.00 -53.78   0.38    1.00    --  -96.00  88.00 144.00   69
 10  \w    -67.00 -34.70   0.38    1.00    --  -96.00  61.00 120.00   85
 11  \w    -71.00 -22.74   0.38    1.00    --  -96.00  61.00  60.00  127
 12  \w    -51.00 -22.88   0.38    1.00    --  -96.00  45.00 150.00   74
 13  \w    -71.00 -28.06   0.38    1.00    --  -96.00  61.00   0.00  113
 14  \w    -49.00 -19.74   0.38    1.00    --  -96.00  45.00  60.00   77
 15  \w    -51.00 -25.92   0.38    1.00    --  -96.00  45.00 -30.00   66
 16  \w    -51.00 -24.78   0.38    1.00    --  -96.00  45.00 -60.00   69
 17  \w    -51.00 -19.84   0.38    1.00    --  -96.00  45.00 -90.00   82
 18  \w    -51.00 -20.98   0.38    1.00    --  -96.00  45.00-150.00   79
 19  \w    -67.00 -29.00   0.38    1.00    --  -96.00  61.00-120.00  100
 20  \w    -51.00 -24.78   0.38    1.00    --  -96.00  45.00-120.00   69
 21  \w    -98.00 -42.90   0.38    1.00    --  -96.00  77.00 -60.00  145
 22  \w    -42.00  34.00   0.38    0.48    --  -43.70  37.00 -90.00  200
 23  \w    -49.00 -22.78   0.38    1.00    --  -96.00  45.00   0.00   69
 24  \w    -46.00 -20.54   0.38    1.00    --  -96.00  45.00  90.00   67
 25  \w   -113.00 -76.14   0.38    0.48    --  -43.70 -57.00 -30.00   97
 26  \w   -167.00-140.02   0.38    1.00    --  -96.00 -88.00  27.00   71
 27  \w   -133.00 -81.70   0.38    1.00    --  -96.00 -88.00  27.00  135
 28  \w    -70.00 -32.00   0.38    0.48    --  -43.70 -57.00 -30.00  100
 29  \w     38.00 103.36   0.38    1.00    --  109.23 -94.00-150.00  172
 30  \w    -17.00  40.00   0.38    0.48    --   43.70 -88.00  27.00  150
 31  \w    105.00 140.72   0.38    1.00    --  109.23 -88.00  27.00   94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0376525000
_diffrn_orient_matrix_UB_12      0.0056569000
_diffrn_orient_matrix_UB_13      0.0615767000
_diffrn_orient_matrix_UB_21      -0.0363932000
_diffrn_orient_matrix_UB_22      0.1042782000
_diffrn_orient_matrix_UB_23      -0.0287796000
_diffrn_orient_matrix_UB_31      -0.0801429000
_diffrn_orient_matrix_UB_32      -0.0498221000
_diffrn_orient_matrix_UB_33      -0.0530125000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0290
_diffrn_reflns_av_unetI/netI     0.0277
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.939
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            15156
_diffrn_reflns_point_group_measured_fraction_full 0.647
_diffrn_reflns_point_group_measured_fraction_max 0.600
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.605
_diffrn_reflns_theta_min         4.310
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.932
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54609
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.318
_exptl_crystal_description       block
_exptl_crystal_F_000             1696
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.258
_refine_diff_density_min         -0.235
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 938 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(11)
_refine_ls_extinction_coef       0.0027(2)
_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   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     598
_refine_ls_number_reflns         5113
_refine_ls_number_restraints     11
_refine_ls_restrained_S_all      1.284
_refine_ls_R_factor_all          0.0478
_refine_ls_R_factor_gt           0.0459
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0946P)^2^+0.5094P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1370
_refine_ls_wR_factor_ref         0.1401
_reflns_Friedel_coverage         0.276
_reflns_Friedel_fraction_full    0.295
_reflns_Friedel_fraction_max     0.260
_reflns_number_gt                4761
_reflns_number_total             5113
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc04542k2.cif
_cod_data_source_block           2-dr2-2
_cod_database_code               7132222
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N F'
_shelx_estimated_absorpt_t_max   0.904
_shelx_estimated_absorpt_t_min   0.873
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 N2-C45
 1.45 with sigma of 0.01
 O3-C13 = O3-C14
 1.39 with sigma of 0.01
 O8A-C29 = O8-C29
 1.09 with sigma of 0.01
 O8-C29 = O8A-C29
 0.8 with sigma of 0.01
 N2-C37 \\sim N2-C45
 with sigma of 0.02
 O8-C29 \\sim O8A-C29
 with sigma of 0.02
3. Others
 Sof(C43)=Sof(H43)=Sof(C44)=Sof(H44)=Sof(C45)=Sof(C46)=Sof(H46)=Sof(C47)=
 Sof(H47)=Sof(C48)=Sof(H48)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(C50)=Sof(H50A)=
 Sof(H50B)=Sof(H50C)=1-FVAR(1)
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C39)=
 Sof(H39)=Sof(C40)=Sof(H40)=Sof(C41)=Sof(H41)=Sof(C42)=Sof(H42)=Sof(C37)=
 Sof(C38)=Sof(H38)=FVAR(1)
 Fixed Sof: O3(0.5) O3A(0.5) H14C(0.5) H14D(0.5) H14A(0.5) H14B(0.5) O8(0.5)
 O8A(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C14(H14C,H14D), C14(H14A,H14B), C31(H31A,H31B), C35(H35A,
 H35B), C49(H49A,H49B)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2A), C3(H3), C4(H4), C5(H5), C17(H17), C18(H18), C19(H19), C20(H20),
 C21(H21), C23(H23), C24(H24), C25(H25), C26(H26), C39(H39), C40(H40), C41(H41),
  C42(H42), C38(H38), C43(H43), C44(H44), C46(H46), C47(H47), C48(H48)
4.c Fitted hexagon refined as free rotating group:
 C27(C22,C23,C24,C25,C26), C39(C40,C41,C42,C37,C38)
4.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C15(H15A,H15B,H15C), C30(H30A,H30B,H30C), C36(H36A,H36B,
 H36C), C50(H50A,H50B,H50C)
4.e Idealised tetrahedral OH refined as rotating group:
 O2(H2), O7(H7)
;
_shelx_res_checksum              55435
_shelx_hkl_checksum              70865
_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 1.781
_oxdiff_exptl_absorpt_empirical_full_min 0.462