Highly efficient regio-selective ring-opening nucleophilic fluorination of aziridines and azetidines: access to β- or γ-fluorinated amino acid derivatives.
Zhu, Liping; Xiong, Jiale; An, Junkai; Chen, Nannan; Xue, Jijun; Jiang, Xianxing; Organic & biomolecular chemistry 17 (2019) 3797–3804; doi:10.1039/c9ob00172g

data_7156733
_publ_section_title
;
 Highly efficient regio-selective ring-opening nucleophilic fluorination
 of aziridines and azetidines: access to \b- or \g-fluorinated amino acid
 derivatives.
;
_journal_issue                   15
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3797
_journal_page_last               3804
_journal_paper_doi               10.1039/c9ob00172g
_journal_volume                  17
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C15 H19 F N2 O6'
_chemical_formula_sum            'C15 H19 F N2 O6'
_chemical_formula_weight         342.32
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-12-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-12-26 deposited with the CCDC.    2019-03-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.6350(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.10300(10)
_cell_length_b                   24.0246(3)
_cell_length_c                   13.7034(2)
_cell_measurement_reflns_used    8132
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.0800
_cell_measurement_theta_min      3.6380
_cell_volume                     1660.96(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (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 5.2913
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.983
_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    -64.00  12.00   1.00    1.00    --  -41.14  38.00 -60.00   76
  2  \w    -66.00  27.00   1.00    1.00    --  -41.14  38.00  30.00   93
  3  \w   -111.00 -26.00   1.00    1.00    --  -41.14 -38.00-150.00   85
  4  \w     25.00  97.00   1.00    1.00    --   41.14-125.00 150.00   72
  5  \w     79.00 111.00   1.00    1.00    --  106.22-104.00  18.00   32
  6  \w     82.00 169.00   1.00    1.00    --  106.22  30.00-120.00   87
  7  \w     94.00 178.00   1.00    1.00    --  106.22 125.00-120.00   84
  8  \w     34.00 115.00   1.00    1.00    --  106.22-125.00-120.00   81
  9  \w     85.00 178.00   1.00    1.00    --  106.22  61.00   0.00   93
 10  \w     31.00 127.00   1.00    1.00    --  106.22 -77.00-120.00   96
 11  \w     33.00 118.00   1.00    1.00    --  106.22 -45.00 -30.00   85
 12  \w     74.00 168.00   1.00    1.00    --  106.22  77.00 -60.00   94
 13  \w     23.00  49.00   1.00    1.00    --   41.14-125.00 120.00   26
 14  \w     57.00  82.00   1.00    1.00    --   41.14 -99.00-150.00   25
 15  \w      7.00  35.00   1.00    1.00    --   41.14 -99.00-150.00   28
 16  \w    106.00 132.00   1.00    1.00    --  106.22 -15.00-150.00   26
 17  \w     80.00 131.00   1.00    1.00    --  106.22 -30.00   0.00   51
 18  \w     32.00  58.00   1.00    1.00    --  106.22 -30.00   0.00   26
 19  \w     59.00  99.00   1.00    1.00    --  106.22 -94.00  30.00   40
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1486087000
_diffrn_orient_matrix_UB_12      0.0218219000
_diffrn_orient_matrix_UB_13      -0.0987590000
_diffrn_orient_matrix_UB_21      0.1264255000
_diffrn_orient_matrix_UB_22      0.0577549000
_diffrn_orient_matrix_UB_23      0.0217912000
_diffrn_orient_matrix_UB_31      0.2349542000
_diffrn_orient_matrix_UB_32      -0.0172623000
_diffrn_orient_matrix_UB_33      -0.0520044000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0331
_diffrn_reflns_av_unetI/netI     0.0395
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -4
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            12270
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.320
_diffrn_reflns_theta_min         3.680
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.970
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89787
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.369
_exptl_crystal_description       needle
_exptl_crystal_F_000             720
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.152
_refine_diff_density_min         -0.199
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details
;
 Flack x determined using 2780 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.08(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     454
_refine_ls_number_reflns         6438
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0375
_refine_ls_R_factor_gt           0.0360
_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^)+(0.0517P)^2^+0.0830P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0933
_refine_ls_wR_factor_ref         0.0954
_reflns_Friedel_coverage         0.908
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.939
_reflns_number_gt                6214
_reflns_number_total             6438
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob00172g2.cif
_cod_data_source_block           18122410
_cod_depositor_comments          'Adding full bibliography for 7156733.cif.'
_cod_database_code               7156733
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         CHONF
_chemical_oxdiff_usercomment     ZLP-1218
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
O52B \\sim O52A: within 1.7A with sigma of 0.08 and sigma for terminal atoms of
0.16
Uanis(C51B) = Uanis(C51A)
3. Others
 Sof(H42A)=Sof(O52B)=Sof(C51B)=1-FVAR(1)
 Sof(O52A)=Sof(H42)=Sof(C51A)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C12(H12), C42(H42), C42(H42A), C1(H1), C31(H31)
4.b Aromatic/amide H refined with riding coordinates:
 N43(H43), N13(H13), C33(H33), C3(H3), C10(H10), C9(H9), C8(H8), C38(H38),
 C40(H40), C39(H39)
4.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C49(H49A,H49B,
 H49C), C54(H54A,H54B,H54C), C48(H48A,H48B,H48C), C19(H19A,H19B,H19C), C50(H50A,
 H50B,H50C)
;
_shelx_res_checksum              38508
_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 1.153
_oxdiff_exptl_absorpt_empirical_full_min 0.772