Highly Enantioselective Synthesis of Fused Bicyclic Dihydropyranones via Low-loading N-Heterocyclic Carbene Organocatalysis
Li, Jun-Long; Fu, Lu; Wu, Jiao; Yang, Kai-Chuan; Li, Qing-Zhu; Gou, Xiaojun; Peng, Cheng; Han, Bo; Shen, Xu-Dong; Chem. Commun.  (2017) –; doi:10.1039/C7CC02921G

data_7120227
_publ_section_title
;
 Highly Enantioselective Synthesis of Fused Bicyclic Dihydropyranones via
 Low-loading N-Heterocyclic Carbene Organocatalysis
;
_journal_name_full               'Chem. Commun.'
_journal_paper_doi               10.1039/C7CC02921G
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C31 H25 N O3'
_chemical_formula_sum            'C31 H25 N O3'
_chemical_formula_weight         459.52
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-11-11
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_audit_update_record
;
2017-02-15 deposited with the CCDC.
2017-06-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.15832(19)
_cell_length_b                   17.7083(6)
_cell_length_c                   21.1704(6)
_cell_measurement_reflns_used    6058
_cell_measurement_temperature    293.10(10)
_cell_measurement_theta_max      72.7300
_cell_measurement_theta_min      4.8350
_cell_volume                     2308.70(12)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      293.10(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_details
;
  1 omega    1.00   75.00   1.0000    3.0100
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -99.0000  -90.0000 74

  2 omega    1.00   75.00   1.0000    3.0100
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -99.0000  120.0000 74

  3 omega   20.00  104.00   1.0000    3.0100
omega____ theta____ kappa____ phi______ frames
    -       36.2921   57.0000   60.0000 84

  4 omega  -31.00   53.00   1.0000    3.0100
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -57.0000  -60.0000 84

  5 omega  -31.00   53.00   1.0000    3.0100
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -57.0000  150.0000 84

  6 omega   38.00   91.00   1.0000   12.0600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000   90.0000 53

  7 omega   40.00   98.00   1.0000   12.0600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000 -150.0000 58

  8 omega   40.00   98.00   1.0000   12.0600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  -30.0000 58

  9 omega   40.00   98.00   1.0000   12.0600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  -90.0000 58

 10 omega  100.00  178.00   1.0000   12.0600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000 -150.0000 78

 11 omega   38.00   91.00   1.0000   12.0600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  120.0000 53

 12 omega   39.00  109.00   1.0000   12.0600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -180.0000 70

 13 omega   40.00  135.00   1.0000   12.0600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000 -120.0000 95

 14 omega   39.00   95.00   1.0000   12.0600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -41.0000  165.0000 56

 15 omega   10.00  104.00   1.0000    3.0100
omega____ theta____ kappa____ phi______ frames
    -       36.2921   77.0000  150.0000 94

 16 omega   20.00   98.00   1.0000    3.0100
omega____ theta____ kappa____ phi______ frames
    -       36.2921   57.0000  -30.0000 78

 17 omega   20.00  104.00   1.0000    3.0100
omega____ theta____ kappa____ phi______ frames
    -       36.2921   57.0000  -90.0000 84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0618319000
_diffrn_orient_matrix_UB_12      -0.0359348000
_diffrn_orient_matrix_UB_13      -0.0638299000
_diffrn_orient_matrix_UB_21      0.1152418000
_diffrn_orient_matrix_UB_22      0.0736156000
_diffrn_orient_matrix_UB_23      -0.0195490000
_diffrn_orient_matrix_UB_31      0.2131831000
_diffrn_orient_matrix_UB_32      -0.0292586000
_diffrn_orient_matrix_UB_33      0.0290359000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0392
_diffrn_reflns_av_unetI/netI     0.0363
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -4
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            12883
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.797
_diffrn_reflns_theta_min         4.177
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.674
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.33791
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.322
_exptl_crystal_description       plate
_exptl_crystal_F_000             968
_exptl_crystal_size_max          0.65
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.207
_refine_diff_density_min         -0.297
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Flack x determined using 1705 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     316
_refine_ls_number_reflns         4502
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0497
_refine_ls_R_factor_gt           0.0476
_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^)+(0.0949P)^2^+0.0825P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1249
_refine_ls_wR_factor_ref         0.1276
_reflns_Friedel_coverage         0.715
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.963
_reflns_number_gt                4278
_reflns_number_total             4502
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7cc02921g2.cif
_cod_data_source_block           exp_2765
_cod_original_cell_volume        2308.70(13)
_cod_database_code               7120227
_reflns_odcompleteness_completeness 99.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C00B(H00C), C00F(H00F)
2.b Secondary CH2 refined with riding coordinates:
 C00A(H00A,H00B), C00G(H00D,H00E), C00L(H00G,H00L)
2.c Aromatic/amide H refined with riding coordinates:
 C00H(H00H), C00I(H00I), C00J(H00J), C00K(H00K), C00M(H00M), C00N(H00N),
 C00P(H00P), C00Q(H00Q), C00R(H00R), C00S(H00S), C00T(H00T), C00U(H00U),
 C00V(H00V), C00W(H00W), C00X(H00X), C00Y(H00Y), C00Z(H00Z)
;
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-11-11
_olex2_submission_special_instructions 'No special instructions were received'