Effective and novel enantioselective preparation of pyranopyrazoles and pyranocoumarins that is catalyzed by a quinine-derived primary amine.
Yang, Sai; Shen, Liu-Lan; Kim, Yoon-Jung; Jeong, Jin-Hyun; Organic & biomolecular chemistry 14 (2015) 623–630; doi:10.1039/c5ob01656h

data_7154768
_publ_section_title
;
 Effective and novel enantioselective preparation of pyranopyrazoles and
 pyranocoumarins that is catalyzed by a quinine-derived primary amine.
;
_journal_issue                   2
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              623
_journal_page_last               630
_journal_paper_doi               10.1039/c5ob01656h
_journal_volume                  14
_journal_year                    2015
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C25 H19 Cl N2 O'
_chemical_formula_sum            'C25 H19 Cl N2 O'
_chemical_formula_weight         398.87
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_symmetry_space_group_name_Hall  'C 2y'
_symmetry_space_group_name_H-M   'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-10-16
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2015-10-23 deposited with the CCDC.
2015-10-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.747(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.832(2)
_cell_length_b                   5.1765(5)
_cell_length_c                   18.5849(19)
_cell_measurement_reflns_used    6868
_cell_measurement_temperature    303.9
_cell_measurement_theta_max      25.80
_cell_measurement_theta_min      2.26
_cell_volume                     2040.2(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      303.9
_diffrn_measured_fraction_theta_full 0.962
_diffrn_measured_fraction_theta_max 0.962
_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  0.0707
_diffrn_reflns_av_unetI/netI     0.0606
_diffrn_reflns_laue_measured_fraction_full 0.962
_diffrn_reflns_laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            18832
_diffrn_reflns_point_group_measured_fraction_full 0.933
_diffrn_reflns_point_group_measured_fraction_max 0.932
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.018
_diffrn_reflns_theta_min         2.256
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.206
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.4318
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1038 before and 0.0802 after correction.
The Ratio of minimum to maximum transmission is 0.5794.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.299
_exptl_crystal_description       needle
_exptl_crystal_F_000             832
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane ethanol'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.183
_refine_diff_density_min         -0.204
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
;
 Flack x determined using 814 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.14(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     300
_refine_ls_number_reflns         3766
_refine_ls_number_restraints     73
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.1098
_refine_ls_R_factor_gt           0.0650
_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^)+(0.0554P)^2^+2.1117P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1376
_refine_ls_wR_factor_ref         0.1556
_reflns_Friedel_coverage         0.736
_reflns_friedel_fraction_full    0.896
_reflns_friedel_fraction_max     0.895
_reflns_number_gt                2542
_reflns_number_total             3766
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5ob01656h2.cif
_cod_data_source_block           3C
_cod_depositor_comments          'Adding full bibliography for 7154768.cif.'
_cod_original_cell_volume        2040.2(4)
_cod_database_code               7154768
_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. Rigid body (RIGU) restrains
 C14, C17, C15, C16, C18, C19, C26, C27, C28, C29
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.001
3. Others
 Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28)=Sof(C29)=Sof(H29)=1-
 FVAR(1)
 Sof(C15)=Sof(H15)=Sof(C16)=Sof(H16)=Sof(C18)=Sof(H18)=Sof(C19)=Sof(H19)=FVAR(1)
 Fixed Sof: H17A(0.5) H17(0.5)
4.a Ternary CH refined with riding coordinates:
 C4(H4)
4.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C9(H9), C10(H10), C12(H12), C13(H13), C17(H17A), C17(H17), C21(H21),
 C22(H22), C23(H23), C24(H24), C25(H25), C15(H15), C16(H16), C18(H18), C19(H19),
  C26(H26), C27(H27), C28(H28), C29(H29)
4.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_shelx_res_checksum              5677
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'