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_7159530
_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 unk
_chemical_formula_moiety         'C41 H32 Cl N4 O5, 2(C H2 Cl2)'
_chemical_formula_sum            'C43 H36 Cl5 N4 O5'
_chemical_formula_weight         866.01
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-01-06
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-01-06 deposited with the CCDC.	2023-08-14 downloaded from the CCDC.
;
_cell_angle_alpha                70.975(3)
_cell_angle_beta                 81.134(3)
_cell_angle_gamma                85.203(3)
_cell_formula_units_Z            1
_cell_length_a                   9.8337(10)
_cell_length_b                   10.0674(10)
_cell_length_c                   11.4250(11)
_cell_measurement_reflns_used    9959
_cell_measurement_temperature    272.0
_cell_measurement_theta_max      26.381
_cell_measurement_theta_min      2.369
_cell_volume                     1055.84(18)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      272.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.996
_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  0.0438
_diffrn_reflns_av_unetI/netI     0.0601
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            24859
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.460
_diffrn_reflns_theta_min         2.370
_diffrn_source_current           0.0
_diffrn_source_power             0.0
_diffrn_source_voltage           0.0
_exptl_absorpt_coefficient_mu    0.393
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6702
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1544 before and 0.0898 after correction.
The Ratio of minimum to maximum transmission is 0.8991.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.362
_exptl_crystal_description       block
_exptl_crystal_F_000             447
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.323
_refine_diff_density_min         -0.286
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 2149 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   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     522
_refine_ls_number_reflns         8548
_refine_ls_number_restraints     91
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.1034
_refine_ls_R_factor_gt           0.0663
_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^)+(0.0549P)^2^+0.6109P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1356
_refine_ls_wR_factor_ref         0.1498
_reflns_Friedel_coverage         0.961
_reflns_Friedel_fraction_full    0.967
_reflns_Friedel_fraction_max     0.957
_reflns_number_gt                5973
_reflns_number_total             8548
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob01098h2.cif
_cod_data_source_block           1_CCDC1
_cod_depositor_comments
'Adding full bibliography for 7159529--7159530.cif.'
_cod_database_code               7159530
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.891
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl1-C1 \\sim Cl1A-C1
 with sigma of 0.02
 Cl-C1 \\sim ClA-C1
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Cl1A \\sim Cl1 \\sim C1 \\sim Cl \\sim ClA: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C01J \\sim C01G \\sim C00W \\sim C01F \\sim C01D \\sim C01C: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 Cl, C1, Cl1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Cl1A, ClA, C1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(H1BC)=Sof(H1BD)=Sof(Cl1A)=Sof(ClA)=1-FVAR(1)
 Sof(Cl1)=Sof(Cl)=Sof(H1AB)=Sof(H1AA)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C00P(H00B,H00C), C00S(H00D,H00E), C01K(H01M,H01N), C1(H1AB,H1AA), C1(H1BC,H1BD)
6.b Aromatic/amide H refined with riding coordinates:
 N009(H009), N00A(H00A), C00M(H00M), C00U(H00U), C00V(H00V), C00Y(H00Y),
 C00Z(H00Z), C010(H010), C011(H011), C012(H012), C013(H013), C014(H014),
 C015(H015), C016(H016), C017(H017), C018(H018), C01A(H01A), C01B(H01B),
 C01G(H01G), C01J(H01J), C01C(H01F), C01D(H01H), C01F(H01I), C01H(H01K),
 C01I(H01L)
6.c Fitted hexagon refined as free rotating group:
 C01G(C01J,C01C,C01D,C01F,C00W)
6.d Idealised Me refined as rotating group:
 C01E(H01C,H01D,H01E)
;
_shelx_res_checksum              54237
_olex2_submission_special_instructions 'No special instructions were received'