Squaramide-catalyzed asymmetric regioselective allylic alkylation of 4-aminopyrazolones with Morita-Baylis-Hillman carbonates.
Xue, Aiqi; Wei, Shiqiang; Wei, Xingfu; Huang, Yue; Qu, Jingping; Wang, Baomin; Organic & biomolecular chemistry 21 (2023) 7173–7179; doi:10.1039/d3ob01098h

data_7159529
_publ_section_title
;
 Squaramide-catalyzed asymmetric regioselective allylic alkylation of
 4-aminopyrazolones with Morita-Baylis-Hillman carbonates.
;
_journal_issue                   35
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              7173
_journal_page_last               7179
_journal_paper_doi               10.1039/d3ob01098h
_journal_volume                  21
_journal_year                    2023
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C25 H21 N3 O4 S'
_chemical_formula_sum            'C25 H21 N3 O4 S'
_chemical_formula_weight         459.51
_space_group_crystal_system      tetragonal
_space_group_IT_number           78
_space_group_name_Hall           'P 4cw'
_space_group_name_H-M_alt        'P 43'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-06-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-06-24 deposited with the CCDC.	2023-08-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.7405(7)
_cell_length_b                   11.7405(7)
_cell_length_c                   16.9107(15)
_cell_measurement_reflns_used    5914
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      29.593
_cell_measurement_theta_min      2.454
_cell_volume                     2331.0(3)
_computing_cell_refinement       'SAINT V8.40A (?, 2016)'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'SAINT V8.40A (?, 2016)'
_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_temperature      298.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0375
_diffrn_reflns_av_unetI/netI     0.0426
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            14634
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.663
_diffrn_reflns_theta_min         2.112
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    0.175
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.6707
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1595 before and 0.0698 after correction. The Ratio of minimum to maximum transmission is 0.8991. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.309
_exptl_crystal_description       needle
_exptl_crystal_F_000             960
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_exptl_transmission_factor_max   0.7460
_exptl_transmission_factor_min   0.6707
_refine_diff_density_max         0.464
_refine_diff_density_min         -0.435
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.1(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     304
_refine_ls_number_reflns         4416
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0895
_refine_ls_R_factor_gt           0.0580
_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^)+(0.1147P)^2^+0.1424P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1527
_refine_ls_wR_factor_ref         0.1722
_reflns_Friedel_coverage         0.931
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                3186
_reflns_number_total             4416
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob01098h2.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 7159529--7159530.cif.'
_cod_database_code               7159529
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.993
_shelx_estimated_absorpt_t_min   0.933
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9(2)
 0.1(2)
2. 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
3. Rigid bond restraints
 C004, C00O
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4.a Secondary CH2 refined with riding coordinates:
 C00I(H00A,H00B)
4.b Aromatic/amide H refined with riding coordinates:
 C004(H004), C00K(H00K), C00L(H00L), C00M(H00M), C00N(H00N), C00O(H00O),
 C00P(H00P), C00Q(H00Q), C00R(H00R), C00T(H00T), C00V(H00V), C00W(H00W),
 C00X(H00X)
4.c X=CH2 refined with riding coordinates:
 C00S(H00C,H00D)
4.d Idealised Me refined as rotating group:
 C00U(H00E,H00F,H00G)
;
_shelx_res_checksum              91136
_olex2_submission_special_instructions 'No special instructions were received'