Direct construction of chiral quaternary dihydropyranones through highly enantioselective organocatalytic hetero-Diels–Alder reactions of olefinic azlactones
Gao, Tai-Ping; Liu, Dan; Lin, Jun-Bing; Hu, Xiu-Qin; Wang, Zhu-Yin; Xu, Peng-Fei; Organic Chemistry Frontiers 3 (2016) 598–; doi:10.1039/C6QO00018E

data_1553419
_publ_section_title
;
 Direct construction of chiral quaternary dihydropyranones through highly
 enantioselective organocatalytic hetero-Diels--Alder reactions of
 olefinic azlactones
;
_journal_issue                   5
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              598
_journal_paper_doi               10.1039/C6QO00018E
_journal_volume                  3
_journal_year                    2016
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C28 H22 F3 N O5'
_chemical_formula_sum            'C28 H22 F3 N O5'
_chemical_formula_weight         509.47
_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   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-11-13
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_audit_update_record
;
2015-03-18 deposited with the CCDC.
2016-03-03 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   9.1158(3)
_cell_length_b                   9.8126(3)
_cell_length_c                   28.3116(9)
_cell_measurement_reflns_used    1269
_cell_measurement_temperature    294.29(10)
_cell_measurement_theta_max      57.7080
_cell_measurement_theta_min      5.0920
_cell_volume                     2532.46(14)
_computing_cell_refinement
'CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58)'
_computing_data_collection
'CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58)'
_computing_data_reduction
'CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      294.29(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_details
;
  1 omega  -73.00  -25.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -19.0000 -120.0000 48

  2 omega    9.00   40.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -19.0000 -120.0000 31

  3 omega   69.00  123.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000 -150.0000 54

  4 omega   68.00   95.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000 -125.0000 -180.0000 27

  5 omega   50.00   98.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -99.0000  -90.0000 48

  6 omega    4.00   76.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -57.0000   60.0000 72

  7 omega   46.00   84.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000 -180.0000 38

  8 omega   36.00  143.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -91.0000   30.0000 107

  9 omega   41.00   69.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000 -120.0000 28

 10 omega   60.00   93.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000   60.0000 33

 11 omega  126.00  177.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   50.0000 -180.0000 51

 12 omega   36.00   93.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000  120.0000 57
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0984981000
_diffrn_orient_matrix_UB_12      0.0438086000
_diffrn_orient_matrix_UB_13      0.0415333000
_diffrn_orient_matrix_UB_21      -0.0068246000
_diffrn_orient_matrix_UB_22      0.1456739000
_diffrn_orient_matrix_UB_23      -0.0201664000
_diffrn_orient_matrix_UB_31      -0.1371518000
_diffrn_orient_matrix_UB_32      -0.0387886000
_diffrn_orient_matrix_UB_33      -0.0288069000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0315
_diffrn_reflns_av_unetI/netI     0.0552
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            6121
_diffrn_reflns_theta_full        69.72
_diffrn_reflns_theta_max         69.72
_diffrn_reflns_theta_min         4.77
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.903
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73726
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.336
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             1056
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.138
_refine_diff_density_min         -0.133
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.2(3)
_refine_ls_extinction_coef       0.0035(4)
_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   1.013
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     367
_refine_ls_number_reflns         4094
_refine_ls_number_restraints     48
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0838
_refine_ls_R_factor_gt           0.0533
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0605P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1200
_refine_ls_wR_factor_ref         0.1481
_reflns_number_gt                2681
_reflns_number_total             4094
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c6qo00018e2.cif
_cod_data_source_block           gaotp1112
_cod_original_cell_volume        2532.48(14)
_cod_database_code               1553419
_reflns_odcompleteness_completeness 99.89
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(F1) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F2) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(F3') \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F1) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(F2') \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F1') \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 Fixed Sof: F1'(0.5) F2'(0.5) F3'(0.5) F2(0.5) F1(0.5) F3(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C13(H13A,H13B)
4.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C16(H16), C17(H17), C19(H19),
 C20(H20), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28)
4.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C)
;
_olex2_submission_special_instructions 'No special instructions were received'