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_1571967
_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_absolute_configuration unk
_chemical_formula_moiety         'C29 H25 F7 N2 O4 S2'
_chemical_formula_sum            'C29 H25 F7 N2 O4 S2'
_chemical_formula_weight         662.63
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yac'
_space_group_name_H-M_alt        'P 1 n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-02-01
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2024-02-01 deposited with the CCDC.	2024-06-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.953(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.8892(5)
_cell_length_b                   5.71600(10)
_cell_length_c                   27.6517(7)
_cell_measurement_reflns_used    3688
_cell_measurement_temperature    169.99(10)
_cell_measurement_theta_max      73.2950
_cell_measurement_theta_min      2.4820
_cell_volume                     2840.20(12)
_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      169.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.968
_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    -95.00 -44.00   1.00    1.50    --  -41.11 125.00  90.00   51
  2  \w   -108.00 -32.00   1.00    1.50    --  -41.11 -38.00  90.00   76
  3  \w   -113.00 -13.00   1.00    1.50    --  -41.11 -57.00   0.00  100
  4  \w     80.00 105.00   1.00    2.00    --  106.95  30.00 -60.00   25
  5  \w    132.00 169.00   1.00    2.00    --  106.95  30.00 -60.00   37
  6  \w    125.00 171.00   1.00    2.00    --  106.95 125.00   0.00   46
  7  \w     57.00 178.00   1.00    2.00    --  106.95  15.00-120.00  121
  8  \w     38.00 105.00   1.00    2.00    --  106.95 -94.00   0.00   67
  9  \w     34.00 103.00   1.00    2.00    --  106.95 -45.00  60.00   69
 10  \w     30.00  88.00   1.00    2.00    --  106.95 -94.00 -60.00   58
;
_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      -0.0038061000
_diffrn_orient_matrix_UB_12      0.0170033000
_diffrn_orient_matrix_UB_13      0.0547569000
_diffrn_orient_matrix_UB_21      -0.0831387000
_diffrn_orient_matrix_UB_22      0.0641448000
_diffrn_orient_matrix_UB_23      -0.0207803000
_diffrn_orient_matrix_UB_31      -0.0206171000
_diffrn_orient_matrix_UB_32      -0.2611022000
_diffrn_orient_matrix_UB_33      -0.0014301000
_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  0.0445
_diffrn_reflns_av_unetI/netI     0.0676
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            10438
_diffrn_reflns_point_group_measured_fraction_full 0.684
_diffrn_reflns_point_group_measured_fraction_max 0.653
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.534
_diffrn_reflns_theta_min         2.514
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.480
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60188
_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            'clear light colourless'
_exptl_crystal_density_diffrn    1.550
_exptl_crystal_description       block
_exptl_crystal_F_000             1360
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.396
_refine_diff_density_min         -0.445
_refine_diff_density_rms         0.077
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.05(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     791
_refine_ls_number_reflns         7478
_refine_ls_number_restraints     740
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.0679
_refine_ls_R_factor_gt           0.0538
_refine_ls_shift/su_max          0.008
_refine_ls_shift/su_mean         0.003
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0762P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1347
_refine_ls_wR_factor_ref         0.1506
_reflns_Friedel_coverage         0.349
_reflns_Friedel_fraction_full    0.368
_reflns_Friedel_fraction_max     0.339
_reflns_number_gt                5937
_reflns_number_total             7478
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03230f2.cif
_cod_data_source_block           3022-5
_cod_depositor_comments
'Adding full bibliography for 1571965--1571967.cif.'
_cod_database_code               1571967
_shelx_shelxl_version_number     2018/3
_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. Rigid bond restraints
 S2, C16
 with sigma for 1-2 distances of 0.0008 and sigma for 1-3 distances of 0.0008
 S3, C30
 with sigma for 1-2 distances of 0.0008 and sigma for 1-3 distances of 0.0008
3. Uiso/Uaniso restraints and constraints
S1 \\sim N1: within 2A with sigma of 0.0006 and sigma for terminal atoms of
0.0012 within 2A
N2 \\sim S2: within 2A with sigma of 0.0006 and sigma for terminal atoms of
0.0012 within 2A
N4 \\sim S4: within 2A with sigma of 0.0006 and sigma for terminal atoms of
0.0012 within 2A
S3 \\sim N3: within 2A with sigma of 0.0006 and sigma for terminal atoms of
0.0012 within 2A
S2 \\sim C16: within 2A with sigma of 0.000008 and sigma for terminal atoms of
0.000016 within 2A
C30 \\sim S3: within 2A with sigma of 0.0008 and sigma for terminal atoms of
0.0016 within 2A
Uanis(C13) \\sim Ueq: with sigma of 0.0007 and sigma for terminal atoms of
0.0014
Uanis(C51) \\sim Ueq: with sigma of 0.0009 and sigma for terminal atoms of
0.0018
Uanis(S2) = Uanis(C16)
4. Rigid body (RIGU) restrains
 C49, S3, O6, O5, N3, C30, C40, C37, C35, C31, C41, C45, H37A, H37B, C38, H35,
 C34, H31, C32, F8, C42, C46, N4, H38A, H38B, C39, H34, C33, H32, F9, C43, C47,
 C51, S4, H39A, H39B, C36, F10, F11, C44, C48, H47, H51, C50, O7, O8, C52, H36A,
  H36B, H36C, F13, F12, F14, H48, H50, C53, C56, H49, H53, C54, C57, H56, H54,
 C55, H57, C58, H58A, H58B, H58C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.006
 C9, S1, O2, O1, N1, C23, C1, C8, C24, C27, C2, C11, H8A, H8B, H24, C25, C28,
 H27, C3, C7, N2, C12, C10, H9A, H9B, H25, C26, H28, H3, C4, H7, C19, S2, F2,
 C13, H10A, H10B, C29, C22, H4, H19, O3, O4, C16, C14, F1, H29A, H29B, H29C,
 H22, C20, C17, F4, C15, F3, H20, C21, C18, H17, F7, F6, F5, H21, C6, H18, C5,
 H5A, H5B, H5C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.006
5.a Secondary CH2 refined with riding coordinates:
 C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B), C8(H8A,H8B), C10(H10A,H10B),
 C9(H9A,H9B)
5.b Aromatic/amide H refined with riding coordinates:
 C24(H24), C50(H50), C35(H35), C53(H53), C3(H3), C7(H7), C34(H34), C54(H54),
 C20(H20), C22(H22), C48(H48), C31(H31), C25(H25), C47(H47), C51(H51), C21(H21),
  C32(H32), C4(H4), C57(H57), C28(H28), C49(H49), C27(H27), C18(H18), C19(H19),
 C17(H17), C56(H56)
5.c Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C58(H58A,H58B,H58C), C5(H5A,H5B,H5C), C29(H29A,H29B,H29C)
;
_shelx_res_checksum              63716
_shelx_hkl_checksum              43738
_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 1.525
_oxdiff_exptl_absorpt_empirical_full_min 0.662