Fluorine-induced diastereodivergence discovered in an equally rare enantioselective syn-aza-Henry reaction
Bing, Jade A.; Schley, Nathan D.; Johnston, Jeffrey N.; Chemical Science  (2022) –; doi:10.1039/D1SC05910F

data_1566352
_publ_section_title
;
 Fluorine-induced diastereodivergence discovered in an equally rare
 enantioselective syn-aza-Henry reaction
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC05910F
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C17 H23 F N2 O4'
_chemical_formula_sum            'C17 H23 F N2 O4'
_chemical_formula_weight         338.37
_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             2019-08-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-10-26 deposited with the CCDC.	2022-02-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.1130(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.32624(13)
_cell_length_b                   15.5828(2)
_cell_length_c                   11.74267(16)
_cell_measurement_reflns_used    13960
_cell_measurement_temperature    99.98(10)
_cell_measurement_theta_max      72.1280
_cell_measurement_theta_min      3.9090
_cell_volume                     1815.31(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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      99.98(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1506
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.979
_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   -108.00  -7.00   1.00    1.00    --  -36.45 -19.00  60.00  101
  2  \w   -104.00 -20.00   1.00    1.00    --  -36.45 -57.00 -90.00   84
  3  \w   -106.00 -18.00   1.00    1.00    --  -36.45 -38.00  30.00   88
  4  \w   -106.00  33.00   1.00    1.00    --  -36.45   0.00 120.00  139
  5  \w     23.00  90.00   1.00    1.00    --   36.45-125.00  60.00   67
  6  \w    -33.00  55.00   1.00    1.00    --   36.45 -38.00-120.00   88
  7  \w     23.00  90.00   1.00    1.00    --   36.45-125.00-180.00   67
  8  \w     18.00 106.00   1.00    1.00    --   36.45  38.00  90.00   88
  9  \w     10.00 104.00   1.00    1.00    --   36.45  77.00  30.00   94
 10  \w     91.00 176.00   1.00    3.00    --  108.65  61.00  90.00   85
 11  \w     82.00 176.00   1.00    3.00    --  108.65  77.00   0.00   94
 12  \w     82.00 176.00   1.00    3.00    --  108.65  77.00  30.00   94
 13  \w     82.00 176.00   1.00    3.00    --  108.65  77.00  60.00   94
 14  \w     39.00 115.00   1.00    3.00    --  108.65-111.00 -30.00   76
 15  \w     41.00 135.00   1.00    3.00    --  108.65 -77.00 150.00   94
 16  \w     82.00 176.00   1.00    3.00    --  108.65  77.00  90.00   94
 17  \w     39.00 109.00   1.00    3.00    --  108.65 -94.00-150.00   70
 18  \w     87.00 178.00   1.00    3.00    --  108.65  30.00 150.00   91
 19  \w     39.00 109.00   1.00    3.00    --  108.65 -94.00  30.00   70
 20  \w     87.00 178.00   1.00    3.00    --  108.65  30.00  60.00   91
 21  \w     87.00 178.00   1.00    3.00    --  108.65  30.00 120.00   91
 22  \w     39.00 109.00   1.00    3.00    --  108.65 -94.00 120.00   70
 23  \w     91.00 176.00   1.00    3.00    --  108.65  61.00 120.00   85
 24  \w     91.00 176.00   1.00    3.00    --  108.65  61.00  60.00   85
 25  \w     42.00 127.00   1.00    3.00    --  108.65 -61.00 -60.00   85
 26  \w     70.00 178.00   1.00    3.00    --  108.65  15.00-180.00  108
 27  \w     91.00 176.00   1.00    3.00    --  108.65  61.00 -30.00   85
 28  \w     91.00 177.00   1.00    3.00    --  108.65  45.00  90.00   86
 29  \w     87.00 178.00   1.00    3.00    --  108.65  30.00  90.00   91
 30  \w     91.00 177.00   1.00    3.00    --  108.65  45.00  30.00   86
 31  \w     91.00 177.00   1.00    3.00    --  108.65  45.00  60.00   86
 32  \w     91.00 177.00   1.00    3.00    --  108.65  45.00 150.00   86
 33  \w     82.00 176.00   1.00    3.00    --  108.65  77.00 120.00   94
 34  \w    -33.00  49.00   1.00    1.00    --   36.45 -38.00 120.00   82
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0983944000
_diffrn_orient_matrix_UB_12      -0.0097210000
_diffrn_orient_matrix_UB_13      -0.1247005000
_diffrn_orient_matrix_UB_21      -0.0944651000
_diffrn_orient_matrix_UB_22      0.0668841000
_diffrn_orient_matrix_UB_23      0.0314861000
_diffrn_orient_matrix_UB_31      0.0742039000
_diffrn_orient_matrix_UB_32      0.0721435000
_diffrn_orient_matrix_UB_33      -0.0459553000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0290
_diffrn_reflns_av_unetI/netI     0.0298
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            24691
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.947
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.965
_diffrn_reflns_theta_min         3.918
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.794
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.811
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
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    1.238
_exptl_crystal_description       block
_exptl_crystal_F_000             720
_exptl_crystal_size_max          0.189
_exptl_crystal_size_mid          0.158
_exptl_crystal_size_min          0.101
_refine_diff_density_max         0.187
_refine_diff_density_min         -0.207
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 2905 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     458
_refine_ls_number_reflns         6879
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0307
_refine_ls_R_factor_gt           0.0273
_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^)+(0.0289P)^2^+0.3462P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0640
_refine_ls_wR_factor_ref         0.0687
_reflns_Friedel_coverage         0.863
_reflns_Friedel_fraction_full    0.953
_reflns_Friedel_fraction_max     0.913
_reflns_number_gt                6613
_reflns_number_total             6879
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc05910f2.cif
_cod_data_source_block           jab-1-299
_cod_original_cell_volume        1815.30(4)
_cod_database_code               1566352
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C17H23FN2O4
_reflns_odcompleteness_completeness 99.97
_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 C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(H5AC)=Sof(H5AD)=Sof(C6B)=Sof(H6B)=Sof(C7B)=Sof(H7BA)=Sof(H7BB)=1-FVAR(1)
 Sof(H5AA)=Sof(H5AB)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C2(H2B), C2A(H2AA)
3.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B), C4A(H4AA,H4AB), C5A(H5AA,H5AB), C5A(H5AC,H5AD)
3.c Aromatic/amide H refined with riding coordinates:
 N2(H2), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12), N2A(H2A), C6A(H6A),
 C9A(H9A), C10A(H10A), C11A(H11A), C12A(H12A), C13A(H13A), C6B(H6B), C00W(H00W)
3.d X=CH2 refined with riding coordinates:
 C7(H7A,H7B), C7A(H7AA,H7AB), C7B(H7BA,H7BB)
3.e Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15D,H15E,H15F), C16(H16D,H16E,H16F), C15A(H15A,H15B,
 H15C), C16A(H16A,H16B,H16C), C17A(H17A,H17B,H17C)
;
_shelx_res_checksum              93547
_shelx_hkl_checksum              76042
_olex2_date_sample_data_collection 2019-08-05
_olex2_exptl_crystal_mounting_method 'mounted in a polyimide loop'
_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 1.476
_oxdiff_exptl_absorpt_empirical_full_min 0.866