Organocatalytic asymmetric synthesis of quaternary α-isoxazole-α-alkynylamino acid derivatives
Li, Min; Chen, Yihua; Yan, Yinkun; Liu, Min; Huang, Min; Li, Wenzhe; Cao, Lianyi; Zhang, Xiao-Mei; Organic & Biomolecular Chemistry  (2022) –; doi:10.1039/D2OB01746F

data_7158956
_publ_section_title
;
 Organocatalytic asymmetric synthesis of quaternary
 \a-isoxazole-\a-alkynylamino acid derivatives
;
_journal_name_full               'Organic &amp; Biomolecular Chemistry'
_journal_paper_doi               10.1039/D2OB01746F
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C28 H31 N3 O5'
_chemical_formula_sum            'C28 H31 N3 O5'
_chemical_formula_weight         489.56
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2020-12-31
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-02-28 deposited with the CCDC.	2022-10-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.5012(5)
_cell_length_b                   17.0320(7)
_cell_length_c                   18.9074(10)
_cell_measurement_reflns_used    2869
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      67.6570
_cell_measurement_theta_min      5.1770
_cell_volume                     2737.6(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.987
_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   -102.00 -26.00   1.00    2.00    --  -33.50 -77.00  90.00   76
  2  \w    -62.00   1.00   1.00    2.00    --  -33.50  77.00-180.00   63
  3  \w    -82.00 -32.00   1.00    2.00    --  -33.50 178.00 120.00   50
  4  \w     70.00 105.00   1.00    2.00    --   36.47 178.00  30.00   35
  5  \w     58.00 110.00   1.00    2.00    --   36.47 178.00-180.00   52
  6  \w     42.00  67.00   1.00    2.00    --   36.47 -99.00  90.00   25
  7  \w     32.00  58.00   1.00    2.00    --   36.47  57.00-150.00   26
  8  \w     74.00 101.00   1.00    2.00    --   36.47  57.00-150.00   27
  9  \w     12.00  38.00   1.00    2.00    --   36.47 -99.00  90.00   26
 10  \w     81.00 107.00   1.00    2.00    --   36.47 178.00 -60.00   26
 11  \w     42.00  68.00   1.00   13.00    --  108.00 -94.00  90.00   26
 12  \w    112.00 177.00   1.00   13.00    --  108.00 111.00 -60.00   65
 13  \w     38.00 110.00   1.00   13.00    --  108.00 -94.00   0.00   72
 14  \w     49.00 102.00   1.00   13.00    --  108.00 -61.00  60.00   53
 15  \w    122.00 178.00   1.00   13.00    --  108.00 111.00  60.00   56
 16  \w     50.00 132.00   1.00   13.00    --  108.00 -30.00 120.00   82
 17  \w     72.00 100.00   1.00   13.00    --  108.00 -94.00 150.00   28
 18  \w     63.00  89.00   1.00   13.00    --  108.00 -95.00 -85.00   26
 19  \w     51.00 128.00   1.00   13.00    --  108.00 -30.00 -30.00   77
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1448656000
_diffrn_orient_matrix_UB_12      -0.0189623000
_diffrn_orient_matrix_UB_13      -0.0458578000
_diffrn_orient_matrix_UB_21      0.0860251000
_diffrn_orient_matrix_UB_22      0.0319446000
_diffrn_orient_matrix_UB_23      -0.0656952000
_diffrn_orient_matrix_UB_31      0.0666950000
_diffrn_orient_matrix_UB_32      -0.0824656000
_diffrn_orient_matrix_UB_33      -0.0148900000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0324
_diffrn_reflns_av_unetI/netI     0.0440
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            10617
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.777
_diffrn_reflns_theta_min         3.493
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.669
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77583
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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    1.188
_exptl_crystal_description       block
_exptl_crystal_F_000             1040
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.206
_refine_diff_density_min         -0.138
_refine_diff_density_rms         0.029
_refine_ls_abs_structure_details
;
 Flack x determined using 1323 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.04(17)
_refine_ls_extinction_coef       0.0028(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     355
_refine_ls_number_reflns         5157
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0658
_refine_ls_R_factor_gt           0.0486
_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^)+(0.0604P)^2^+0.1837P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1219
_refine_ls_wR_factor_ref         0.1393
_reflns_Friedel_coverage         0.745
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.966
_reflns_number_gt                3979
_reflns_number_total             5157
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ob01746f2.cif
_cod_data_source_block           202012316
_cod_original_cell_volume        2737.7(2)
_cod_database_code               7158956
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C30H3O3N4
_chemical_oxdiff_usercomment     r
_shelx_estimated_absorpt_t_max   0.936
_shelx_estimated_absorpt_t_min   0.895
_reflns_odcompleteness_completeness 99.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C19A-C20A
 1.55 with sigma of 0.02
 H2A-N2
 0.87 with sigma of 0.02
 N3-H3A
 0.87 with sigma of 0.02
 C22-C23
 1.65 with sigma of 0.02
 C22A-C23A
 1.65 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C22) = Uanis(C22A)
Uanis(C23) = Uanis(C23A)
Uanis(C19) = Uanis(C19A)
Uanis(C20) = Uanis(C20A)
4. Others
 Sof(C22A)=Sof(H22C)=Sof(H22D)=Sof(C23A)=Sof(H23D)=Sof(H23E)=Sof(H23F)=1-FVAR(1)
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(1)
 Sof(C19A)=Sof(H19C)=Sof(H19D)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(2)
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C19A(H19C,H19D), C22(H22A,H22B), C22A(H22C,H22D)
5.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C14(H14), C15(H15), C16(H16),
 C17(H17), C18(H18)
5.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C20A(H20D,H20E,H20F), C23(H23A,H23B,H23C), C23A(H23D,
 H23E,H23F), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C)
;
_shelx_res_checksum              12481
_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 1.357
_oxdiff_exptl_absorpt_empirical_full_min 0.841