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_1566353
_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         'C20 H31 F N2 O4'
_chemical_formula_sum            'C20 H31 F N2 O4'
_chemical_formula_weight         382.47
_space_group_crystal_system      hexagonal
_space_group_IT_number           169
_space_group_name_Hall           'P 61'
_space_group_name_H-M_alt        'P 61'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-08-16
_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                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   11.84190(10)
_cell_length_b                   11.84190(10)
_cell_length_c                   27.22040(10)
_cell_measurement_reflns_used    31810
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      72.1010
_cell_measurement_theta_min      4.2960
_cell_volume                     3305.73(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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1506
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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   -104.00 -10.00   1.00    1.50    --  -36.45 -77.00  90.00   94
  2  \w   -104.00 -20.00   1.00    1.50    --  -36.45 -57.00-150.00   84
  3  \w    -53.00  31.00   1.00    1.50    --  -36.45  57.00-180.00   84
  4  \w   -104.00 -20.00   1.00    1.50    --  -36.45 -57.00 -90.00   84
  5  \w    -31.00  53.00   1.00    1.50    --   36.45 -57.00  60.00   84
  6  \w     18.00 106.00   1.00    1.50    --   36.45  38.00-180.00   88
  7  \w      7.00 108.00   1.00    1.50    --   36.45  19.00-180.00  101
  8  \w     39.00 130.00   1.00    5.00    --  108.65 -30.00 -60.00   91
  9  \w     91.00 176.00   1.00    5.00    --  108.65  61.00 120.00   85
 10  \w     70.00 178.00   1.00    5.00    --  108.65  15.00-180.00  108
 11  \w     91.00 176.00   1.00    5.00    --  108.65  61.00-150.00   85
 12  \w     40.00 126.00   1.00    5.00    --  108.65 -45.00  30.00   86
 13  \w     82.00 176.00   1.00    5.00    --  108.65  77.00  90.00   94
 14  \w     91.00 176.00   1.00    5.00    --  108.65  61.00-120.00   85
 15  \w     91.00 177.00   1.00    5.00    --  108.65  45.00 120.00   86
 16  \w     87.00 178.00   1.00    5.00    --  108.65  30.00 150.00   91
 17  \w     91.00 177.00   1.00    5.00    --  108.65  45.00 150.00   86
 18  \w     82.00 176.00   1.00    5.00    --  108.65  77.00 120.00   94
 19  \w     41.00 135.00   1.00    5.00    --  108.65 -77.00 -30.00   94
 20  \w     70.00 178.00   1.00    5.00    --  108.65  15.00 150.00  108
 21  \w   -104.00 -10.00   1.00    1.50    --  -36.45 -77.00 -30.00   94
 22  \w    -63.00  31.00   1.00    1.50    --  -36.45  77.00-150.00   94
 23  \w   -104.00 -20.00   1.00    1.50    --  -36.45 -57.00   0.00   84
 24  \w    -31.00  53.00   1.00    1.50    --   36.45 -57.00   0.00   84
 25  \w      4.00  34.00   1.00    1.50    --   36.45  87.00 158.59   30
 26  \w    -12.00  70.00   1.00    1.50    --   36.45 -89.00 -60.00   82
 27  \w     91.00 177.00   1.00    5.00    --  108.65  43.00  17.31   86
 28  \w     40.00 143.00   1.00    5.00    --  108.65 -90.00  75.06  103
 29  \w     40.00 142.00   1.00    5.00    --  108.65 -89.00-153.45  102
 30  \w     82.00 176.00   1.00    5.00    --  108.65  77.00 -90.00   94
 31  \w     91.00 177.00   1.00    5.00    --  108.65  45.00  60.00   86
 32  \w     87.00 178.00   1.00    5.00    --  108.65  30.00 -30.00   91
 33  \w     82.00 176.00   1.00    5.00    --  108.65  77.00 -30.00   94
 34  \w     82.00 146.00   1.00    5.00    --  108.65  77.00-180.00   64
 35  \w     41.00 135.00   1.00    5.00    --  108.65 -77.00 150.00   94
;
_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      -0.0773059000
_diffrn_orient_matrix_UB_12      -0.1298605000
_diffrn_orient_matrix_UB_13      -0.0279312000
_diffrn_orient_matrix_UB_21      0.0730726000
_diffrn_orient_matrix_UB_22      -0.0562185000
_diffrn_orient_matrix_UB_23      0.0286138000
_diffrn_orient_matrix_UB_31      -0.1060311000
_diffrn_orient_matrix_UB_32      -0.0503570000
_diffrn_orient_matrix_UB_33      0.0400551000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0349
_diffrn_reflns_av_unetI/netI     0.0141
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            50607
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.268
_diffrn_reflns_theta_min         4.311
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.704
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.580
_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    1.153
_exptl_crystal_description       needle
_exptl_crystal_F_000             1236
_exptl_crystal_size_max          0.415
_exptl_crystal_size_mid          0.077
_exptl_crystal_size_min          0.065
_refine_diff_density_max         0.140
_refine_diff_density_min         -0.148
_refine_diff_density_rms         0.031
_refine_ls_abs_structure_details
;
 Flack x determined using 2063 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     250
_refine_ls_number_reflns         4353
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0235
_refine_ls_R_factor_gt           0.0232
_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^)+(0.0329P)^2^+0.3875P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0584
_refine_ls_wR_factor_ref         0.0586
_reflns_Friedel_coverage         0.951
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                4305
_reflns_number_total             4353
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc05910f2.cif
_cod_data_source_block           jab-bab-6214
_cod_original_cell_volume        3305.73(6)
_cod_database_code               1566353
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C20H31FN2O4
_reflns_odcompleteness_completeness 99.95
_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.a Ternary CH refined with riding coordinates:
 C2(H2)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B), C12(H12A,H12B)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11)
2.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              82192
_shelx_hkl_checksum              22958
_olex2_date_sample_data_collection 2019-08-15
_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 1.174
_oxdiff_exptl_absorpt_empirical_full_min 0.842