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_1566354
_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      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-11-04
_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                90
_cell_formula_units_Z            12
_cell_length_a                   11.50004(6)
_cell_length_b                   18.45454(10)
_cell_length_c                   30.36728(18)
_cell_measurement_reflns_used    24703
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.1420
_cell_measurement_theta_min      2.7800
_cell_volume                     6444.79(6)
_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      100.00(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 0.990
_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    -53.00  31.00   1.00    1.00    --  -36.45  57.00 -90.00   84
  2  \w   -106.00 -18.00   1.00    1.00    --  -36.45 -38.00  30.00   88
  3  \w      1.00  75.00   1.00    1.00    --   36.45 -99.00-150.00   74
  4  \w     20.00 104.00   1.00    1.00    --   36.45  57.00  90.00   84
  5  \w     23.00  90.00   1.00    1.00    --   36.45-125.00  90.00   67
  6  \w     39.00 109.00   1.00    1.00    --  108.65 -94.00  90.00   70
  7  \w     91.00 176.00   1.00    1.00    --  108.65  61.00  60.00   85
  8  \w    100.00 178.00   1.00    1.00    --  108.65 111.00 -60.00   78
  9  \w     39.00 109.00   1.00    1.00    --  108.65 -94.00 -90.00   70
 10  \w     82.00 176.00   1.00    1.00    --  108.65  77.00-180.00   94
 11  \w     91.00 176.00   1.00    1.00    --  108.65  61.00  30.00   85
 12  \w     39.00 109.00   1.00    1.00    --  108.65 -94.00  30.00   70
 13  \w     40.00 126.00   1.00    1.00    --  108.65 -45.00  30.00   86
 14  \w   -104.00 -20.00   1.00    1.00    --  -36.45 -57.00-180.00   84
 15  \w   -104.00 -60.00   1.00    1.00    --  -36.45 -77.00 -60.00   44
;
_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      0.0721841000
_diffrn_orient_matrix_UB_12      0.0684075000
_diffrn_orient_matrix_UB_13      0.0098779000
_diffrn_orient_matrix_UB_21      -0.0323566000
_diffrn_orient_matrix_UB_22      0.0310101000
_diffrn_orient_matrix_UB_23      -0.0454931000
_diffrn_orient_matrix_UB_31      -0.1080427000
_diffrn_orient_matrix_UB_32      0.0364157000
_diffrn_orient_matrix_UB_33      0.0202218000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0245
_diffrn_reflns_av_unetI/netI     0.0250
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            35099
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.268
_diffrn_reflns_theta_min         2.802
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.722
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.340
_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    1.183
_exptl_crystal_description       block
_exptl_crystal_F_000             2472
_exptl_crystal_size_max          0.465
_exptl_crystal_size_mid          0.375
_exptl_crystal_size_min          0.246
_refine_diff_density_max         0.165
_refine_diff_density_min         -0.265
_refine_diff_density_rms         0.057
_refine_ls_abs_structure_details
;
 Flack x determined using 5234 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     748
_refine_ls_number_reflns         12498
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0315
_refine_ls_R_factor_gt           0.0306
_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^)+(0.0423P)^2^+0.9956P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0764
_refine_ls_wR_factor_ref         0.0771
_reflns_Friedel_coverage         0.797
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.971
_reflns_number_gt                12176
_reflns_number_total             12498
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc05910f2.cif
_cod_data_source_block           jab-4-262-d1
_cod_database_code               1566354
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C20H31FN2O4
_reflns_odcompleteness_completeness 99.98
_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), C2B(H2B), C2C(H2C)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B), C11(H11A,H11B), C4B(H4BA,H4BB), C5B(H5BA,H5BB),
 C11B(H11C,H11D), C4C(H4CA,H4CB), C5C(H5CA,H5CB), C11C(H11E,H11F)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C8(H8), C9(H9), C10(H10), C15(H15), C01L(H01L), C7(H7), N1B(H1B),
 C7B(H7B), C8B(H8B), C9B(H9B), C10B(H10B), C1A(H1A), N1C(H1C), C7C(H7C),
 C8C(H8C), C9C(H9C), C10C(H10C)
2.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C1D(H1DA,H1DB,H1DC), C13B(H13D,H13E,H13F),
 C14B(H14D,H14E,H14F), C15B(H15A,H15B,H15C), C17B(H17D,H17E,H17F), C18B(H18D,
 H18E,H18F), C19B(H19D,H19E,H19F), C13C(H13G,H13H,H13I), C14C(H14G,H14H,H14I),
 C15C(H15D,H15E,H15F), C17C(H17G,H17H,H17I), C18C(H18G,H18H,H18I), C19C(H19G,
 H19H,H19I)
;
_shelx_res_checksum              83702
_shelx_hkl_checksum              37630
_olex2_date_sample_data_collection 2019-10-31
_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 1.063
_oxdiff_exptl_absorpt_empirical_full_min 0.903