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_1566356
_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 H32 N2 O4'
_chemical_formula_sum            'C20 H32 N2 O4'
_chemical_formula_weight         364.47
_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             2019-10-07
_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                   11.84105(5)
_cell_length_b                   11.84105(5)
_cell_length_c                   27.02804(15)
_cell_measurement_reflns_used    39640
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      72.2310
_cell_measurement_theta_min      4.2980
_cell_volume                     3281.90(3)
_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 0.998
_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    -55.00  33.00   1.00    1.00    --  -36.45  38.00  60.00   88
  2  \w   -108.00  -7.00   1.00    1.00    --  -36.45 -19.00 -90.00  101
  3  \w     23.00  90.00   1.00    1.00    --   36.45-125.00  90.00   67
  4  \w    -31.00  53.00   1.00    1.00    --   36.45 -57.00 150.00   84
  5  \w     20.00 104.00   1.00    1.00    --   36.45  57.00  30.00   84
  6  \w     23.00  90.00   1.00    1.00    --   36.45-125.00-180.00   67
  7  \w     20.00 104.00   1.00    1.00    --   36.45  57.00 150.00   84
  8  \w     23.00  90.00   1.00    1.00    --   36.45-125.00  30.00   67
  9  \w     20.00 104.00   1.00    1.00    --   36.45  57.00 -90.00   84
 10  \w     39.00 109.00   1.00    2.23    --  108.65 -94.00 -60.00   70
 11  \w     39.00 109.00   1.00    2.23    --  108.65 -94.00-120.00   70
 12  \w     39.00 109.00   1.00    2.23    --  108.65 -94.00  30.00   70
 13  \w     39.00 130.00   1.00    2.23    --  108.65 -30.00-120.00   91
 14  \w     39.00 115.00   1.00    2.23    --  108.65-111.00 150.00   76
 15  \w     70.00 178.00   1.00    2.23    --  108.65  15.00-150.00  108
 16  \w     91.00 177.00   1.00    2.23    --  108.65  45.00-180.00   86
 17  \w     39.00 178.00   1.00    2.23    --  108.65   0.00 -30.00  139
 18  \w     40.00 126.00   1.00    2.23    --  108.65 -45.00   0.00   86
 19  \w     40.00 126.00   1.00    2.23    --  108.65 -45.00  90.00   86
 20  \w     42.00 127.00   1.00    2.23    --  108.65 -61.00-120.00   85
 21  \w     40.00 126.00   1.00    2.23    --  108.65 -45.00 150.00   86
 22  \w     39.00 115.00   1.00    2.23    --  108.65-111.00-150.00   76
 23  \w     42.00 127.00   1.00    2.23    --  108.65 -61.00   0.00   85
 24  \w    -53.00  31.00   1.00    1.00    --  -36.45  57.00  90.00   84
 25  \w    -31.00  53.00   1.00    1.00    --   36.45 -57.00-120.00   84
 26  \w     10.00 104.00   1.00    1.00    --   36.45  77.00 -60.00   94
 27  \w    -33.00  55.00   1.00    1.00    --   36.45 -38.00 -90.00   88
 28  \w     10.00 104.00   1.00    1.00    --   36.45  77.00-180.00   94
 29  \w     20.00 104.00   1.00    1.00    --   36.45  57.00  90.00   84
 30  \w     70.00 178.00   1.00    2.23    --  108.65  15.00  90.00  108
 31  \w     82.00 176.00   1.00    2.23    --  108.65  77.00 120.00   94
 32  \w     91.00 177.00   1.00    2.23    --  108.65  45.00 -30.00   86
 33  \w     82.00 176.00   1.00    2.23    --  108.65  77.00-150.00   94
 34  \w     82.00 176.00   1.00    2.23    --  108.65  77.00 -90.00   94
 35  \w     87.00 178.00   1.00    2.23    --  108.65  30.00 120.00   91
 36  \w     82.00 176.00   1.00    2.23    --  108.65  77.00-120.00   94
 37  \w     82.00 176.00   1.00    2.23    --  108.65  77.00   0.00   94
 38  \w     82.00 176.00   1.00    2.23    --  108.65  77.00  60.00   94
 39  \w     82.00 176.00   1.00    2.23    --  108.65  77.00-180.00   94
 40  \w     82.00 176.00   1.00    2.23    --  108.65  77.00  30.00   94
 41  \w     91.00 177.00   1.00    2.23    --  108.65  45.00   0.00   86
 42  \w     10.00 104.00   1.00    1.00    --   36.45  77.00  30.00   94
 43  \w     10.00 104.00   1.00    1.00    --   36.45  77.00 -90.00   94
 44  \w     23.00  90.00   1.00    1.00    --   36.45-125.00-120.00   67
 45  \w     10.00 104.00   1.00    1.00    --   36.45  77.00  90.00   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      0.0783614000
_diffrn_orient_matrix_UB_12      0.1502438000
_diffrn_orient_matrix_UB_13      0.0004024000
_diffrn_orient_matrix_UB_21      -0.1056174000
_diffrn_orient_matrix_UB_22      0.0025281000
_diffrn_orient_matrix_UB_23      0.0324706000
_diffrn_orient_matrix_UB_31      0.0725380000
_diffrn_orient_matrix_UB_32      -0.0030592000
_diffrn_orient_matrix_UB_33      0.0468276000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0423
_diffrn_reflns_av_unetI/netI     0.0149
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_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       -31
_diffrn_reflns_number            62164
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.350
_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    0.618
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.474
_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    1.106
_exptl_crystal_description       prism
_exptl_crystal_F_000             1188
_exptl_crystal_size_max          0.346
_exptl_crystal_size_mid          0.152
_exptl_crystal_size_min          0.107
_refine_diff_density_max         0.160
_refine_diff_density_min         -0.140
_refine_diff_density_rms         0.027
_refine_ls_abs_structure_details
;
 Flack x determined using 1965 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     241
_refine_ls_number_reflns         4242
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0278
_refine_ls_R_factor_gt           0.0276
_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^)+(0.0424P)^2^+0.3618P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0742
_refine_ls_wR_factor_ref         0.0744
_reflns_Friedel_coverage         0.914
_reflns_Friedel_fraction_full    0.960
_reflns_Friedel_fraction_max     0.954
_reflns_number_gt                4213
_reflns_number_total             4242
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc05910f2.cif
_cod_data_source_block           jab-4-237
_cod_database_code               1566356
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C20H32N2O4
_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), C3(H3)
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              46156
_shelx_hkl_checksum              86588
_olex2_date_sample_data_collection 2019-10-07
_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 1.289
_oxdiff_exptl_absorpt_empirical_full_min 0.879