Enantioselective synthesis of spiro[indoline-3,4'-pyrano[2,3-c]pyrazole] derivatives via an organocatalytic asymmetric Michael/cyclization cascade reaction.
Xie, Jin; Xing, Xiao-Yu; Sha, Feng; Wu, Zhi-Yan; Wu, Xin-Yan; Organic & biomolecular chemistry 14 (2016) 8346–8355; doi:10.1039/c6ob01256f

data_7155236
_publ_section_title
;
 Enantioselective synthesis of spiro[indoline-3,4'-pyrano[2,3-c]pyrazole]
 derivatives via an organocatalytic asymmetric Michael/cyclization cascade
 reaction.
;
_journal_issue                   35
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              8346
_journal_page_last               8355
_journal_paper_doi               10.1039/c6ob01256f
_journal_volume                  14
_journal_year                    2016
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C43 H32 Br N5 O3'
_chemical_formula_sum            'C43 H32 Br N5 O3'
_chemical_formula_weight         746.64
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-10-23
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_audit_update_record
;
2016-03-15 deposited with the CCDC.
2016-08-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.527(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.218(2)
_cell_length_b                   16.657(3)
_cell_length_c                   16.344(3)
_cell_measurement_reflns_used    3563
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      20.730
_cell_measurement_theta_min      2.293
_cell_volume                     3595.0(11)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0554
_diffrn_reflns_av_unetI/netI     0.1414
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            29858
_diffrn_reflns_point_group_measured_fraction_full 0.968
_diffrn_reflns_point_group_measured_fraction_max 0.945
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.705
_diffrn_reflns_theta_min         1.542
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.192
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6136
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0817 before and 0.0648 after correction.
The Ratio of minimum to maximum transmission is 0.8230.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.379
_exptl_crystal_description       block
_exptl_crystal_F_000             1536
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.287
_refine_diff_density_min         -0.263
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 2776 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.003(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.866
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     941
_refine_ls_number_reflns         15941
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.866
_refine_ls_R_factor_all          0.1338
_refine_ls_R_factor_gt           0.0474
_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^)] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0811
_refine_ls_wR_factor_ref         0.1057
_reflns_Friedel_coverage         0.844
_reflns_Friedel_fraction_full    0.933
_reflns_Friedel_fraction_max     0.896
_reflns_number_gt                8148
_reflns_number_total             15941
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6ob01256f2.cif
_cod_data_source_block           mo_dm15790_0m
_cod_depositor_comments          'Adding full bibliography for 7155236.cif.'
_cod_original_cell_volume        3595.2(10)
_cod_database_code               7155236
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.911
_shelx_estimated_absorpt_t_min   0.841
_olex2_refinement_description
;
1. 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
2.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C60(H60A,H60B)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C7(H7), C16(H16), C21(H21), C22(H22), C23(H23), C24(H24),
 C25(H25), C27(H27), C28(H28), C29(H29), C30(H30), C31(H31), C33(H33), C34(H34),
  C35(H35), C36(H36), C37(H37), C39(H39), C40(H40), C41(H41), C42(H42),
 C43(H43), C47(H47), C48(H48), C50(H50), C59(H59), C63(H63), C64(H64), C65(H65),
  C66(H66), C67(H67), C70(H70), C71(H71), C72(H72), C73(H73), C74(H74),
 C76(H76), C77(H77), C78(H78), C79(H79), C80(H80), C82(H82), C83(H83), C84(H84),
  C85(H85), C86(H86)
2.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C18(H18A,H18B,H18C), C52(H52A,H52B,H52C), C61(H61A,H61B,H61C)
;
_shelx_res_checksum              7732
_olex2_submission_special_instructions 'No special instructions were received'