Asymmetric synthesis of spiro[chroman-3,3′-pyrazol] scaffolds with an all-carbon quaternary stereocenter via a oxa-Michael–Michael cascade strategy with bifunctional amine-thiourea organocatalysts
Zheng, Weiping; Zhang, Jiayong; Liu, Shuang; Yu, Chengbin; Miao, Zhiwei; RSC Advances 5 (2015) 91108–; doi:10.1039/C5RA17792H

data_7235983
_publ_section_title
;
 Asymmetric synthesis of spiro[chroman-3,3&#x2032;-pyrazol] scaffolds with
 an all-carbon quaternary stereocenter via a oxa-Michael--Michael cascade
 strategy with bifunctional amine-thiourea organocatalysts
;
_journal_issue                   111
_journal_name_full               'RSC Advances'
_journal_page_first              91108
_journal_paper_doi               10.1039/C5RA17792H
_journal_volume                  5
_journal_year                    2015
_chemical_absolute_configuration 'CHOOSE rm ad rmad syn or unk'
_chemical_compound_source        'Fidalrestat,Sorbinil,Catechln and so on'
_chemical_formula_moiety         'C29 H31 N3 O5'
_chemical_formula_sum            'C29 H31 N3 O5'
_chemical_formula_weight         501.57
_chemical_melting_point          427.5(5)
_chemical_name_common            NO
_chemical_name_systematic
'(2R,3R,4R)-3'-Methyl-4-(nitromethyl)-1',2-diphenyl spiro[chroman-3,4'-pyrazol]-5'(1'H)-one'
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014/7
_audit_update_record
;
2015-09-30 deposited with the CCDC.
2015-10-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.6366(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.007(4)
_cell_length_b                   13.691(4)
_cell_length_c                   11.577(4)
_cell_measurement_reflns_used    914
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      77.60
_cell_measurement_theta_min      30.10
_cell_volume                     1317.6(8)
_computing_cell_refinement       'CrystalClear-SM Expert 2.1 b42'
_computing_data_collection       'CrystalClear-SM Expert 2.1 b42 (Rigaku, 2015)'
_computing_data_reduction        'CrystalClear-SM Expert 2.1 b42'
_computing_molecular_graphics    'CrystalStructure 4.1'
_computing_publication_material  'CrystalStructure 4.1 (Rigaku, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'SIR2011 (Burla, et al., 2012)'
_diffrn_ambient_temperature      173(2)
_diffrn_detector_area_resol_mean 5.814
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Rigaku XtaLAB P200'
_diffrn_measurement_method       \w
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54187
_diffrn_reflns_av_R_equivalents  0.0235
_diffrn_reflns_av_unetI/netI     0.0207
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            22397
_diffrn_reflns_point_group_measured_fraction_full 0.868
_diffrn_reflns_point_group_measured_fraction_max 0.854
_diffrn_reflns_theta_full        67.687
_diffrn_reflns_theta_max         77.702
_diffrn_reflns_theta_min         6.228
_exptl_absorpt_coefficient_mu    0.708
_exptl_absorpt_correction_T_max  0.893
_exptl_absorpt_correction_T_min  0.778
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'REQAB (Rigaku, 1998)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.264
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             532
_exptl_crystal_recrystallization_method 'Vapour Deposition'
_exptl_crystal_size_max          0.260
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.160
_refine_diff_density_max         0.208
_refine_diff_density_min         -0.175
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
; 
 Flack x determined using 1818 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   0.00(4)
_refine_ls_extinction_coef       0.0184(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     338
_refine_ls_number_reflns         4797
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0312
_refine_ls_R_factor_gt           0.0309
_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^)+(0.0485P)^2^+0.1527P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0837
_refine_ls_wR_factor_ref         0.0840
_reflns_Friedel_coverage         0.652
_reflns_Friedel_fraction_full    0.728
_reflns_Friedel_fraction_max     0.704
_reflns_number_gt                4707
_reflns_number_total             4797
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5ra17792h2.cif
_cod_data_source_block           shelxl
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value '427-428' was changed to
'427.5(5)' -- the average value was taken and precision was
estimated.

Automatic conversion script
Id: cif_fix_values 6909 2019-04-08 15:41:33Z antanas 
;
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               7235983
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.837
_shelx_estimated_absorpt_t_max   0.895
_shelx_res_checksum              2504