A copper-catalyzed asymmetric Friedel-Crafts hydroxyalkylation of pyrazole-4,5-diones with 5-aminoisoxazoles.
Gao, Siyu; Sun, Xiang; Peng, Sijie; Zha, Zhenggen; Sun, Qi; Wang, Zhiyong; Organic & biomolecular chemistry 22 (2024) 3391–3395; doi:10.1039/d4ob00322e

data_7159886
_publ_section_title
;
 A copper-catalyzed asymmetric Friedel-Crafts hydroxyalkylation of
 pyrazole-4,5-diones with 5-aminoisoxazoles.
;
_journal_issue                   17
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3391
_journal_page_last               3395
_journal_paper_doi               10.1039/d4ob00322e
_journal_volume                  22
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H24 N4 O3'
_chemical_formula_sum            'C23 H24 N4 O3'
_chemical_formula_weight         404.46
_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
_audit_creation_date             2023-09-21
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-02-28 deposited with the CCDC.	2024-04-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.99824(7)
_cell_length_b                   13.13119(9)
_cell_length_c                   17.79770(13)
_cell_measurement_reflns_used    13066
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      72.9810
_cell_measurement_theta_min      4.1590
_cell_volume                     2102.93(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2013/4 (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2169
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_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   -122.00  -1.00   1.00    2.00    --  -41.76 -19.00  30.00  121
  2  \w    -87.00  -6.00   1.00    2.00    --  -41.76 125.00-180.00   81
  3  \w   -116.00 -17.00   1.00    2.00    --  -41.76 -38.00 -60.00   99
  4  \w     80.00 178.00   1.00    4.00    --  106.05  45.00   0.00   98
  5  \w    103.00 178.00   1.00    4.00    --  106.05  77.00  60.00   75
  6  \w     30.00 139.00   1.00    4.00    --  106.05 -77.00-150.00  109
  7  \w     97.00 178.00   1.00    4.00    --  106.05 125.00 -60.00   81
  8  \w    103.00 178.00   1.00    4.00    --  106.05  77.00-160.00   75
  9  \w    103.00 178.00   1.00    4.00    --  106.05  77.00  30.00   75
 10  \w    103.00 178.00   1.00    4.00    --  106.05  77.00 -90.00   75
 11  \w   -116.00 -17.00   1.00    2.00    --  -41.76 -38.00-180.00   99
 12  \w     14.00 115.00   1.00    2.00    --   41.76  57.00 150.00  101
 13  \w      6.00  83.00   1.00    2.00    --   41.76 -99.00  60.00   77
 14  \w     80.00 178.00   1.00    4.00    --  106.05  45.00 150.00   98
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1029699000
_diffrn_orient_matrix_UB_12      0.0714421000
_diffrn_orient_matrix_UB_13      0.0447856000
_diffrn_orient_matrix_UB_21      0.0184975000
_diffrn_orient_matrix_UB_22      -0.0680329000
_diffrn_orient_matrix_UB_23      0.0698888000
_diffrn_orient_matrix_UB_31      0.1354975000
_diffrn_orient_matrix_UB_32      0.0635666000
_diffrn_orient_matrix_UB_33      0.0244816000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0284
_diffrn_reflns_av_unetI/netI     0.0172
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            15262
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.906
_diffrn_reflns_theta_min         4.184
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.701
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61887
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.110a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.277
_exptl_crystal_description       block
_exptl_crystal_F_000             856
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.321
_refine_diff_density_min         -0.228
_refine_diff_density_rms         0.059
_refine_ls_abs_structure_details
;
 Flack x determined using 1699 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.04(6)
_refine_ls_extinction_coef       0.0338(19)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     276
_refine_ls_number_reflns         4132
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0439
_refine_ls_R_factor_gt           0.0434
_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^)+(0.0688P)^2^+0.3457P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1143
_refine_ls_wR_factor_ref         0.1151
_reflns_Friedel_coverage         0.732
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.968
_reflns_number_gt                4059
_reflns_number_total             4132
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob00322e2.cif
_cod_data_source_block           scd-gsy2023-0706_auto
_cod_depositor_comments          'Adding full bibliography for 7159886.cif.'
_cod_database_code               7159886
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         C20H20N2O2
_shelx_estimated_absorpt_t_max   0.884
_shelx_estimated_absorpt_t_min   0.861
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1.a Ternary CH refined with riding coordinates:
 C13(H13)
1.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B)
1.c Aromatic/amide H refined with riding coordinates:
 N4(H4), C23(H23), C19(H19), C12(H12), C20(H20), C10(H10), C11(H11), C22(H22),
 C9(H9), C8(H8), C21(H21)
1.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C14(H14A,H14B,H14C), C17(H17A,H17B,H17C)
1.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              36984
_shelx_hkl_checksum              81794
_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 1.470
_oxdiff_exptl_absorpt_empirical_full_min 0.674