Organocatalytic and enantioselective [4+2] cyclization between hydroxymaleimides and <i>ortho</i>-hydroxyphenyl <i>para</i>-quinone methide-selective preparation of chiral hemiketals.
Xiang, Min; Li, Chen-Yi; Song, Xiang-Jia; Zou, Ying; Huang, Zhi-Cheng; Li, Xia; Tian, Fang; Wang, Li-Xin; Chemical communications (Cambridge, England) 56 (2020) 14825–14828; doi:10.1039/d0cc06777f

data_7127462
_publ_section_title
;
 Organocatalytic and enantioselective [4+2] cyclization between
 hydroxymaleimides and <i>ortho</i>-hydroxyphenyl <i>para</i>-quinone
 methide-selective preparation of chiral hemiketals.
;
_journal_issue                   94
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              14825
_journal_page_last               14828
_journal_paper_doi               10.1039/d0cc06777f
_journal_volume                  56
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C33 H37 N O5'
_chemical_formula_sum            'C33 H37 N O5'
_chemical_formula_weight         527.63
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2019-07-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-03-18 deposited with the CCDC.	2020-10-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 115.500(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.2748(4)
_cell_length_b                   14.2248(3)
_cell_length_c                   10.9525(3)
_cell_measurement_reflns_used    4337
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.7700
_cell_measurement_theta_min      4.4850
_cell_volume                     1444.84(9)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
  1 omega  -52.00   35.00   0.5000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000   57.0000    0.0000 174

  2 omega  -50.00   -4.00   0.5000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000   57.0000   60.0000 92

  3 omega -101.00  -20.00   0.5000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -57.0000 -150.0000 162

  4 omega   57.00  101.00   0.5000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000 -120.0000 88

  5 omega   74.00  106.00   0.5000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   77.0000 -180.0000 64

  6 omega   71.00  108.00   0.5000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000  150.0000 74

  7 omega   57.00  106.00   0.5000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000   90.0000 98

  8 omega   20.00   46.00   0.5000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   77.0000  -60.0000 52

  9 omega   18.00   58.00   0.5000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   77.0000 -180.0000 80

 10 omega   18.00   82.00   0.5000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   57.0000   30.0000 128

 11 omega   18.00   62.00   0.5000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -19.0000   60.0000 88

 12 omega   61.00  100.00   0.5000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   77.0000  -60.0000 78

 13 omega  -27.00   18.00   0.5000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -57.0000   60.0000 90

 14 omega  -27.00   13.00   0.5000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -19.0000   60.0000 80

 15 omega   57.00  107.00   0.5000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000    0.0000 100

 16 omega   59.00  109.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -120.0000 100

 17 omega   57.00  109.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  -30.0000 104

 18 omega   39.00   96.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000   90.0000 114

 19 omega   88.00  177.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000  120.0000 178

 20 omega   63.00  141.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  178.0000  -60.0000 156

 21 omega  146.00  178.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000 -180.0000 64

 22 omega   66.00   97.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000 -180.0000 62

 23 omega   67.00   99.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  150.0000 64

 24 omega   56.00   90.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000 -120.0000 68

 25 omega  142.00  171.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000 -180.0000 58

 26 omega   89.00  169.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000   30.0000 160

 27 omega   86.00  111.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000   60.0000 50

 28 omega   38.00   99.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000 -180.0000 122

 29 omega   85.00  111.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000 -180.0000 52

 30 omega   56.00  120.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000  -60.0000 128

 31 omega   99.00  126.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000  -30.0000 54

 32 omega   82.00  167.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   60.0000 170

 33 omega   82.00  136.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000 -180.0000 108

 34 omega  133.00  176.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  150.0000 86
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0117010000
_diffrn_orient_matrix_UB_12      -0.0962327000
_diffrn_orient_matrix_UB_13      0.0685028000
_diffrn_orient_matrix_UB_21      0.1625236000
_diffrn_orient_matrix_UB_22      0.0163564000
_diffrn_orient_matrix_UB_23      0.0858789000
_diffrn_orient_matrix_UB_31      -0.0326358000
_diffrn_orient_matrix_UB_32      0.0469324000
_diffrn_orient_matrix_UB_33      0.1104710000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0297
_diffrn_reflns_av_unetI/netI     0.0395
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            10407
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.075
_diffrn_reflns_theta_max         67.075
_diffrn_reflns_theta_min         4.473
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.648
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81666
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.213
_exptl_crystal_description       block
_exptl_crystal_F_000             564
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.222
_refine_diff_density_min         -0.152
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 1920 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.05(14)
_refine_ls_extinction_coef       0.0029(6)
_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   1.049
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     362
_refine_ls_number_reflns         5148
_refine_ls_number_restraints     51
_refine_ls_restrained_S_all      1.106
_refine_ls_R_factor_all          0.0486
_refine_ls_R_factor_gt           0.0436
_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^)+(0.0663P)^2^+0.0215P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1149
_refine_ls_wR_factor_ref         0.1214
_reflns_Friedel_coverage         0.914
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                4645
_reflns_number_total             5148
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc06777f2.cif
_cod_data_source_block           201907173a
_cod_original_cell_volume        1444.85(8)
_cod_database_code               7127462
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C20H20N4O4
_shelx_estimated_absorpt_t_max   0.938
_shelx_estimated_absorpt_t_min   0.909
_reflns_odcompleteness_completeness 99.96
_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, All O(H) groups
2. Rigid bond restraints
 C2, O3
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C9, O3
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(C8) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C11)
\\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C9) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C2) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(C9) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
4.a Riding coordinates:
 O5(H5)
4.b Ternary CH refined with riding coordinates:
 C7(H7)
4.c Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B)
4.d Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13), C15(H15), C19(H19), C29(H29),
 C30(H30), C31(H31), C32(H32), C33(H33)
4.e Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C)
4.f Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_olex2_submission_special_instructions 'No special instructions were received'