Organocatalytic asymmetric [4 + 1] annulation of in situ generated ortho-quinomethanes with 4-halo pyrazolones: straightforward access to chiral spiro-benzofuran pyrazolones
Chu, Ming-Ming; Qi, Suo-Suo; Wang, Yi-Feng; Wang, Biao; Jiang, Zhen-Hui; Xu, Dan-Qian; Xu, Zhen-Yuan; Organic Chemistry Frontiers 6 (2019) 1977–; doi:10.1039/C9QO00332K

data_1554868
_publ_section_title
;
 Organocatalytic asymmetric [4 + 1] annulation of in situ generated
 ortho-quinomethanes with 4-halo pyrazolones: straightforward access to
 chiral spiro-benzofuran pyrazolones
;
_journal_issue                   12
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              1977
_journal_paper_doi               10.1039/C9QO00332K
_journal_volume                  6
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_compound_source        synthesis
_chemical_formula_moiety         'pyrazolone, phenyl'
_chemical_formula_sum            'C24 H19 Cl N2 O3'
_chemical_formula_weight         418.86
_chemical_melting_point          412
_chemical_name_common            4-spiropyrazolone
_chemical_name_systematic
3-(4-chlorophenyl)-7-methoxy-3'-methyl-1'-phenyl-3H-spiro[benzofuran-2,4'-pyrazol]-5'(1'H)-one
_chemical_properties_physical    stable
_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_method           SHELXL-2013
_audit_update_record
;
2018-09-11 deposited with the CCDC.	2019-04-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.9309(6)
_cell_length_b                   17.470(2)
_cell_length_c                   19.675(3)
_cell_measurement_reflns_used    7745
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      53.756
_cell_measurement_theta_min      4.663
_cell_volume                     2038.6(4)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_diffrn_ambient_temperature      173(2)
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0808
_diffrn_reflns_av_unetI/netI     0.0560
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            19157
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.493
_diffrn_reflns_theta_min         2.376
_exptl_absorpt_coefficient_mu    0.216
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5341
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.365
_exptl_crystal_description       prismatic
_exptl_crystal_F_000             872
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CH2Cl2 and CH3OH'
_exptl_crystal_size_max          0.180
_exptl_crystal_size_mid          0.160
_exptl_crystal_size_min          0.110
_refine_diff_density_max         0.399
_refine_diff_density_min         -0.590
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
; 
 Flack x determined using 1210 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons and Flack (2004), Acta Cryst. A60, s61). 
;
_refine_ls_abs_structure_Flack   0.10(4)
_refine_ls_extinction_coef       0.019(6)
_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   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     274
_refine_ls_number_reflns         3774
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0663
_refine_ls_R_factor_gt           0.0585
_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^)+(0.0770P)^2^+0.8588P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1544
_refine_ls_wR_factor_ref         0.1624
_reflns_Friedel_coverage         0.719
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                3301
_reflns_number_total             3774
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9qo00332k2.cif
_cod_data_source_block           mo_dd18130_0m
_cod_database_code               1554868
_shelx_estimated_absorpt_t_min   0.962
_shelx_estimated_absorpt_t_max   0.977
_shelxl_version_number           2013-4
_shelx_res_checksum              22836