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_1571965
_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         'C21 H18 Br F7 N2'
_chemical_formula_sum            'C21 H18 Br F7 N2'
_chemical_formula_weight         511.28
_chemical_name_systematic        CXQ-220602-2
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-06-02
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-06-02 deposited with the CCDC.	2024-06-23 downloaded from the CCDC.
;
_cell_angle_alpha                80.233(4)
_cell_angle_beta                 78.910(4)
_cell_angle_gamma                79.201(4)
_cell_formula_units_Z            2
_cell_length_a                   9.0199(4)
_cell_length_b                   9.6664(5)
_cell_length_c                   12.1317(5)
_cell_measurement_reflns_used    6279
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      74.7700
_cell_measurement_theta_min      3.8030
_cell_volume                     1009.79(8)
_computing_cell_refinement       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (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      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.977
_diffrn_measured_fraction_theta_max 0.964
_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     20.00  67.12   0.38    0.04    --   43.34  49.00 -77.00  124
  2  \w     74.00 102.88   0.38    0.04    --   43.34  49.00 -77.00   76
  3  \w    126.00 173.88   0.38    0.10    --  109.59  45.00-150.00  126
  4  \w    122.00 176.34   0.38    0.10    --  109.59  61.00-120.00  143
  5  \w     87.00 176.30   0.38    0.10    --  109.59  49.00 -77.00  235
  6  \w    102.00 127.08   0.38    0.10    --  109.59  45.00 -30.00   66
  7  \w    132.00 177.22   0.38    0.10    --  109.59  45.00 -30.00  119
  8  \w     88.00 173.12   0.38    0.10    --  109.59  45.00   0.00  224
  9  \w    -78.00 -44.94   0.38    0.10    --  -96.00  77.00-180.00   87
 10  \w    -55.00 -19.66   0.38    0.10    --  -96.00  49.00 -77.00   93
 11  \w    -59.00 -28.98   0.38    0.10    --  -96.00  61.00 -60.00   79
 12  \w    -47.00 -18.88   0.38    0.10    --  -96.00  45.00  90.00   74
 13  \w    -51.00 -25.92   0.38    0.10    --  -96.00  45.00 120.00   66
 14  \w    -50.00 -21.88   0.38    0.10    --  -96.00  45.00 150.00   74
 15  \w    -25.00  35.04   0.38    0.04    --  -43.34  19.00  30.00  158
 16  \w    -11.00  33.46   0.38    0.04    --  -43.34  37.00  60.00  117
 17  \w    -45.00  31.00   0.38    0.04    --  -43.34  49.00 -77.00  200
 18  \w     40.00  69.64   0.38    0.10    --  109.59 -61.00 -90.00   78
 19  \w     93.00 147.34   0.38    0.10    --  109.59 125.00 120.00  143
 20  \w      1.00  27.22   0.38    0.04    --   43.34 -49.00 135.00   69
 21  \w     37.00  65.12   0.38    0.10    --  109.59 -61.00 150.00   74
 22  \w     52.00  99.88   0.38    0.10    --  109.59 -94.00  60.00  126
 23  \w     90.00 115.08   0.38    0.10    --  109.59-125.00  60.00   66
 24  \w     68.00 103.72   0.38    0.10    --  109.59-125.00   0.00   94
 25  \w     37.00  98.56   0.38    0.04    --   43.34-125.00 -60.00  162
 26  \w     71.00 115.08   0.38    0.10    --  109.59-125.00-180.00  116
 27  \w     45.00 104.28   0.38    0.10    --  109.59-125.00-120.00  156
 28  \w     38.00 106.02   0.38    0.10    --  109.59 -94.00-120.00  179
 29  \w    -87.00 -31.14   0.38    0.10    --  -96.00 125.00   0.00  147
 30  \w    -86.00 -40.78   0.38    0.10    --  -96.00 125.00 -30.00  119
 31  \w    -56.00 -28.64   0.38    0.04    --  -43.34 -49.00 135.00   72
 32  \w   -116.00 -55.96   0.38    0.04    --  -43.34 -49.00 135.00  158
 33  \w   -159.00-132.02   0.38    0.10    --  -96.00 -49.00 135.00   71
 34  \w   -115.00 -72.06   0.38    0.10    --  -96.00 -49.00 135.00  113
;
_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      -0.1294223000
_diffrn_orient_matrix_UB_12      0.0115089000
_diffrn_orient_matrix_UB_13      -0.0690717000
_diffrn_orient_matrix_UB_21      0.0085511000
_diffrn_orient_matrix_UB_22      0.1590348000
_diffrn_orient_matrix_UB_23      -0.0382766000
_diffrn_orient_matrix_UB_31      0.1194337000
_diffrn_orient_matrix_UB_32      -0.0376109000
_diffrn_orient_matrix_UB_33      -0.1041018000
_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  0.0275
_diffrn_reflns_av_unetI/netI     0.0308
_diffrn_reflns_Laue_measured_fraction_full 0.977
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            8740
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.966
_diffrn_reflns_theta_min         3.749
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.472
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80804
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.110a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear whiteish white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.682
_exptl_crystal_description       needle
_exptl_crystal_F_000             512
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.328
_refine_diff_density_min         -0.421
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     280
_refine_ls_number_reflns         3689
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0271
_refine_ls_R_factor_gt           0.0260
_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^)+(0.0299P)^2^+0.5241P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0653
_refine_ls_wR_factor_ref         0.0662
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3530
_reflns_number_total             3689
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03230f2.cif
_cod_data_source_block           zyw-220602-2_auto
_cod_depositor_comments
'Adding full bibliography for 1571965--1571967.cif.'
_cod_database_code               1571965
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C N F Br'
_shelx_estimated_absorpt_t_max   0.723
_shelx_estimated_absorpt_t_min   0.723
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C00N(H00A,H00B), C00O(H00C,H00D), C00P(H00F,H00G), C00R(H00H,H00K), C00S(H00L,
 H00N), C00T(H00O,H00P), C00U(H00Q,H00R)
2.b Aromatic/amide H refined with riding coordinates:
 C00E(H00E), C00I(H00I), C00J(H00J), C00M(H00M)
;
_shelx_res_checksum              74037
_shelx_hkl_checksum              40129
_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 1.401
_oxdiff_exptl_absorpt_empirical_full_min 0.686