Four-component defluorinative reaction of allylic fluorides, amidines, and Cs2CO3 under transition-metal-free conditions
Chen, Yu-Lan; Sun, Li-Wen; Chen, Jia-Wei; Zhu, Ming-Quan; Ma, Mengtao; Shen, Zhi-Liang; Chu, Xue-Qiang; Green Chemistry 24 (2022) 6816–6822; doi:10.1039/D2GC02045A

data_7245608
_publ_section_title
;
 Four-component defluorinative reaction of allylic fluorides, amidines,
 and Cs2CO3 under transition-metal-free conditions
;
_journal_issue                   18
_journal_name_full               'Green Chemistry'
_journal_page_first              6816
_journal_page_last               6822
_journal_paper_doi               10.1039/D2GC02045A
_journal_volume                  24
_journal_year                    2022
_chemical_formula_moiety         'C28 H27 F7 N4 O4'
_chemical_formula_sum            'C28 H27 F7 N4 O4'
_chemical_formula_weight         616.53
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-12-31
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2021-12-31 deposited with the CCDC.	2022-08-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.565(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.8007(8)
_cell_length_b                   19.4570(18)
_cell_length_c                   15.5025(12)
_cell_measurement_reflns_used    4777
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      26.3160
_cell_measurement_theta_min      2.4710
_cell_volume                     2915.1(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_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 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  41.00   1.00    2.00    --  -11.35  77.00   0.00   80
  2  \w    -20.00  25.00   1.00    2.00    --   11.90  77.00-150.00   45
  3  \w      8.00  87.00   1.00    2.00    --   11.90  77.00-120.00   79
  4  \w     40.00  66.00   1.00    6.00    --   11.90-178.00-120.00   26
  5  \w     61.00  86.00   1.00    4.00    --   11.90  37.00  90.00   25
  6  \w     61.00  82.00   1.00    4.00    --   11.90  37.00  90.00   21
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0315383000
_diffrn_orient_matrix_UB_12      -0.0048263000
_diffrn_orient_matrix_UB_13      -0.0376146000
_diffrn_orient_matrix_UB_21      -0.0078038000
_diffrn_orient_matrix_UB_22      -0.0360350000
_diffrn_orient_matrix_UB_23      0.0035519000
_diffrn_orient_matrix_UB_31      -0.0658861000
_diffrn_orient_matrix_UB_32      0.0021068000
_diffrn_orient_matrix_UB_33      -0.0269114000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1115
_diffrn_reflns_av_unetI/netI     0.1485
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            16749
_diffrn_reflns_point_group_measured_fraction_full 0.899
_diffrn_reflns_point_group_measured_fraction_max 0.899
_diffrn_reflns_theta_full        24.994
_diffrn_reflns_theta_max         24.994
_diffrn_reflns_theta_min         2.093
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.125
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67032
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
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    1.405
_exptl_crystal_description       block
_exptl_crystal_F_000             1272
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.409
_refine_diff_density_min         -0.370
_refine_diff_density_rms         0.088
_refine_ls_abs_structure_details
;
 Flack x determined using 1246 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -1.8(10)
_refine_ls_extinction_coef       0.0058(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.005
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     812
_refine_ls_number_reflns         9243
_refine_ls_number_restraints     61
_refine_ls_restrained_S_all      1.006
_refine_ls_R_factor_all          0.1359
_refine_ls_R_factor_gt           0.0926
_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^)+(0.1273P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2199
_refine_ls_wR_factor_ref         0.2673
_reflns_Friedel_coverage         0.742
_reflns_Friedel_fraction_full    0.792
_reflns_Friedel_fraction_max     0.792
_reflns_number_gt                5283
_reflns_number_total             9243
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2gc02045a2.cif
_cod_data_source_block           9209
_cod_database_code               7245608
_shelx_shelxl_version_number     2017/1
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F17-C43 \\sim F12-C43
 with sigma of 0.02
 F13-C43 \\sim F14-C43
 with sigma of 0.02
 F15-C43 \\sim F16-C43
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 F13, F15, F17, C42, C43
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F12, F14, F16, C42, C43
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Others
 Sof(F12)=Sof(F14)=Sof(F16)=1-FVAR(1)
 Sof(F13)=Sof(F15)=Sof(F17)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C24(H24A,H24B), C35(H35A,H35B), C55(H55A,H55B)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C15(H15), C19(H19), C20(H20), C21(H21),
 C22(H22), C30(H30), C31(H31), C32(H32), C33(H33), C39(H39), C50(H50), C51(H51),
  C52(H52), C53(H53)
5.c X=CH2 refined with riding coordinates:
 N1(H1A,H1B), N8(H8A,H8B)
5.d Idealised Me refined as rotating group:
 C8(H8C,H8D,H8E), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C25(H25A,H25B,
 H25C), C36(H36A,H36B,H36C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C56(H56A,
 H56B,H56C)
;
_shelx_res_checksum              99625
_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 4.917
_oxdiff_exptl_absorpt_empirical_full_min 0.381