Chemo-, regio-, and stereoselective tetrafunctionalization of fluoroalkynes enables divergent synthesis of 5-7-membered azacycles.
Chen, Jia-Wei; Ji, Wen-Jun; Huang, Xue-Ying; Ge, Danhua; Shen, Zhi-Liang; Guo, Kai; Chu, Xue-Qiang; Chemical science 15 (2024) 12026–12035; doi:10.1039/d4sc03230f

data_1571966
_publ_section_title
;
 Chemo-, regio-, and stereoselective tetrafunctionalization of
 fluoroalkynes enables divergent synthesis of 5-7-membered azacycles.
;
_journal_issue                   30
_journal_name_full               'Chemical science'
_journal_page_first              12026
_journal_page_last               12035
_journal_paper_doi               10.1039/d4sc03230f
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         '1(C25 H15 F7 N2 O)'
_chemical_formula_sum            'C25 H15 F7 N2 O'
_chemical_formula_weight         492.39
_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             2023-09-05
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2023-09-05 deposited with the CCDC.	2024-06-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 118.699(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.8721(3)
_cell_length_b                   42.5797(9)
_cell_length_c                   10.9151(3)
_cell_measurement_reflns_used    7411
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.5870
_cell_measurement_theta_min      4.0990
_cell_volume                     4432.2(3)
_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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5368
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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     78.00 111.00   0.75    1.00    --   40.73  38.00  30.00   44
  2  \w     39.00 129.00   0.75    2.50    --  106.95 -61.00 120.00  120
  3  \w     76.00 115.00   0.75    2.50    --  106.95-125.00 -30.00   52
  4  \w     49.00  96.25   0.75    1.00    --   40.73-125.00  60.00   63
  5  \w     34.00 127.00   0.75    2.50    --  106.95 -45.00   0.00  124
  6  \w    142.00 167.50   0.75    2.50    --  106.95  30.00-180.00   34
  7  \w     81.00 106.50   0.75    2.50    --  106.95  30.00-180.00   34
  8  \w   -114.00 -21.75   0.75    1.00    --  -40.73 -38.00 -90.00  123
  9  \w    -52.00  10.25   0.75    1.00    --  -41.23  77.00-180.00   83
 10  \w     34.00  60.25   0.75    1.00    --   41.23-125.00  60.00   35
 11  \w     78.00 107.25   0.75    2.50    --  106.95 -94.00-180.00   39
 12  \w     91.00 118.00   0.75    2.50    --  106.95  45.00  90.00   36
 13  \w    139.00 177.25   0.75    2.50    --  106.95  45.00  90.00   51
 14  \w     37.00  95.50   0.75    2.50    --  106.95 -94.00 -30.00   78
 15  \w     82.00 148.00   0.75    2.50    --  106.95  45.00 -90.00   88
;
_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      0.0618444000
_diffrn_orient_matrix_UB_12      0.0233845000
_diffrn_orient_matrix_UB_13      -0.0635462000
_diffrn_orient_matrix_UB_21      -0.0889560000
_diffrn_orient_matrix_UB_22      0.0265316000
_diffrn_orient_matrix_UB_23      0.0137564000
_diffrn_orient_matrix_UB_31      0.1197918000
_diffrn_orient_matrix_UB_32      0.0076067000
_diffrn_orient_matrix_UB_33      0.1472554000
_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  0.0510
_diffrn_reflns_av_unetI/netI     0.0485
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       50
_diffrn_reflns_limit_k_min       -50
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            18370
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        66.593
_diffrn_reflns_theta_max         66.593
_diffrn_reflns_theta_min         4.153
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.154
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42645
_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            'light colourless'
_exptl_crystal_density_diffrn    1.476
_exptl_crystal_description       block
_exptl_crystal_F_000             2000
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.502
_refine_diff_density_min         -0.451
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.080
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     722
_refine_ls_number_reflns         7804
_refine_ls_number_restraints     694
_refine_ls_restrained_S_all      1.116
_refine_ls_R_factor_all          0.1053
_refine_ls_R_factor_gt           0.0938
_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^)+(0.1422P)^2^+7.7380P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2539
_refine_ls_wR_factor_ref         0.2686
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6511
_reflns_number_total             7804
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03230f2.cif
_cod_data_source_block           1096_2
_cod_depositor_comments
'Adding full bibliography for 1571965--1571967.cif.'
_cod_original_cell_volume        4432.2(2)
_cod_database_code               1571966
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C43-C42
 1.54 with sigma of 0.01
 N2-C20 \\sim N2-C01F
 with sigma of 0.02
 C20-C21 \\sim C01F-C01S
 with sigma of 0.02
 C20-C25 \\sim C01F-C01U
 with sigma of 0.02
 C23-C24 \\sim C01P-C51
 with sigma of 0.02
 C23-C21 \\sim C01P-C01S
 with sigma of 0.04
 C23-C22 \\sim C01P-C01Y
 with sigma of 0.02
 C24-C22 \\sim C51-C01Y
 with sigma of 0.04
 C21-C22 \\sim C01S-C01Y
 with sigma of 0.02
 C25-C24 \\sim C01U-C51
 with sigma of 0.02
 C23-C25 \\sim C01P-C01U
 with sigma of 0.04
 C21-C25 \\sim C01S-C01U
 with sigma of 0.04
 N2-C21 \\sim N2-C01S
 with sigma of 0.04
 N2-C25 \\sim N2-C01U
 with sigma of 0.04
 C20-C24 \\sim C01F-C51
 with sigma of 0.04
 C20-C22 \\sim C01F-C01Y
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
F6 \\sim C18: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.004 within 2A
F7 \\sim C18: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.004 within 2A
C18 \\sim F5: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.004 within 2A
4. Rigid body (RIGU) restrains
 F10, F12, F8, F13, F14, F11, F16, F9, F17, O2, N4, N3, C26, C27, C28, C29,
 C30, C31, C32, C33, C34, C35, C36, C37, C38, C39, C40, C41, C42, C43, C44, C45,
  C46, C47, C48, C49, C50, C52
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.003
 F4, F3, F1, F6, F7, F5, F2, O1, N1, N2, C1, C01F, C01P, C01S, C01U, C01Y, C2,
 C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19,
 C20, C21, C22, C23, C24, C25, C51
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.004
 F10, F12, F8, F13, F14, F11, F16, F9, F15, F17, O2, N4, N3, C26, C27, C28,
 C29, C30, C31, C32, C33, C34, C35, C36, C37, C38, C39, C40, C41, C42, C43, C44,
  C45, C46, C47, C48, C49, C50, C52
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C01F)=Sof(C01P)=Sof(H01P)=Sof(C01S)=Sof(H01S)=Sof(C01U)=Sof(H01U)=
 Sof(C01Y)=Sof(H01Y)=Sof(C51)=Sof(H51)=Sof(F16)=Sof(F15)=Sof(F17)=Sof(C43)=1-
 FVAR(1)
 Sof(C20)=Sof(C21)=Sof(H21)=Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23)=Sof(C24)=
 Sof(H24)=Sof(C25)=Sof(H25)=Sof(F12)=Sof(F13)=Sof(F14)=Sof(C52)=FVAR(1)
6.a Aromatic/amide H refined with riding coordinates:
 C01P(H01P), C01S(H01S), C01U(H01U), C01Y(H01Y), C2(H2), C3(H3), C4(H4),
 C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C21(H21),
 C22(H22), C23(H23), C24(H24), C25(H25), C51(H51), C27(H27), C28(H28), C29(H29),
  C30(H30), C31(H31), C33(H33), C34(H34), C35(H35), C36(H36), C37(H37),
 C46(H46), C47(H47), C48(H48), C49(H49), C50(H50)
;
_shelx_res_checksum              40951
_shelx_hkl_checksum              15530
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.073
_oxdiff_exptl_absorpt_empirical_full_min 0.457