Asymmetric organocatalytic conjugated addition of pyrazolin-5-ones to ortho-quinomethanes: construction of vicinal tertiary and all-carbon quaternary stereocenters
Chu, Ming-Ming; Qi, Suo-Suo; Ju, Wan-Zhen; Wang, Yi-Feng; Chen, Xue-Yang; Xu, Dan-Qian; Xu, Zhen-Yuan; Organic Chemistry Frontiers 6 (2019) 1140–; doi:10.1039/C9QO00011A

data_1554696
_publ_section_title
;
 Asymmetric organocatalytic conjugated addition of pyrazolin-5-ones to
 ortho-quinomethanes: construction of vicinal tertiary and all-carbon
 quaternary stereocenters
;
_journal_issue                   8
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              1140
_journal_paper_doi               10.1039/C9QO00011A
_journal_volume                  6
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         C31H27ClN2O3,H2O
_chemical_formula_sum            'C31 H29 Cl N2 O4'
_chemical_formula_weight         529.01
_chemical_name_common
(R)-4-benzyl-4-((S)-(4-chlorophenyl)(2-hydroxy-3-methoxyphenyl)methyl)-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one
_chemical_name_systematic
(R)-4-benzyl-4-((S)-(4-chlorophenyl)(2-hydroxy-3-methoxyphenyl)methyl)-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one
_chemical_properties_physical    Heat-sensitive
_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
_audit_creation_method           SHELXL-2013
_audit_update_record
;
2018-10-25 deposited with the CCDC.	2019-02-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.0064(3)
_cell_length_b                   9.7885(3)
_cell_length_c                   30.9078(11)
_cell_measurement_reflns_used    5662
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      50.074
_cell_measurement_theta_min      5.235
_cell_volume                     2724.81(16)
_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      296(2)
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.991
_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  0.0320
_diffrn_reflns_av_unetI/netI     0.0428
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            13582
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.996
_diffrn_reflns_theta_min         2.182
_exptl_absorpt_coefficient_mu    0.179
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6367
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.290
_exptl_crystal_description       prismatic
_exptl_crystal_F_000             1112
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: n-hexane and ethyl acetate'
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.170
_exptl_crystal_size_min          0.140
_refine_diff_density_max         0.202
_refine_diff_density_min         -0.242
_refine_diff_density_rms         0.030
_refine_ls_abs_structure_details
; 
 Flack x determined using 1487 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons and Flack (2004), Acta Cryst. A60, s61). 
;
_refine_ls_abs_structure_Flack   0.02(3)
_refine_ls_extinction_coef       0.030(5)
_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   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     347
_refine_ls_number_reflns         5302
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0615
_refine_ls_R_factor_gt           0.0448
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0536P)^2^+0.2398P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1069
_refine_ls_wR_factor_ref         0.1185
_reflns_Friedel_coverage         0.748
_reflns_Friedel_fraction_full    0.990
_reflns_Friedel_fraction_max     0.990
_reflns_number_gt                4227
_reflns_number_total             5302
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9qo00011a2.cif
_cod_data_source_block           mo_dd18229_0m
_cod_original_cell_volume        2724.80(16)
_cod_database_code               1554696
_shelx_estimated_absorpt_t_min   0.965
_shelx_estimated_absorpt_t_max   0.975
_shelxl_version_number           2013-4
_shelx_res_checksum              35513
_shelx_hkl_checksum              82078