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_7127463
_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_formula_moiety
'C33 H37 N O5, C0.7 H0.7 Cl1.55, C0.3 H0.3 Cl1.45'
_chemical_formula_sum            'C34 H38 Cl3 N O5'
_chemical_formula_weight         647.00
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2019-09-11
_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                98.879(6)
_cell_angle_beta                 105.364(6)
_cell_angle_gamma                95.484(6)
_cell_formula_units_Z            2
_cell_length_a                   10.5380(6)
_cell_length_b                   12.9179(10)
_cell_length_c                   13.0658(9)
_cell_measurement_reflns_used    2830
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.6750
_cell_measurement_theta_min      4.4870
_cell_volume                     1677.0(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -108.00 -32.00   1.00    1.00    --  -33.50 178.00 150.00   76
  2  \w    -62.00  36.00   1.00    1.00    --  -33.50  77.00 120.00   98
  3  \w    -46.00   0.00   1.00    1.00    --  -33.50 -19.00  90.00   46
  4  \w    -86.00 -60.00   1.00    1.00    --  -33.50 -57.00  30.00   26
  5  \w     57.00 109.00   1.00    1.00    --   36.47 178.00  30.00   52
  6  \w     57.00 109.00   1.00    1.00    --   36.47 178.00 120.00   52
  7  \w     18.00 107.00   1.00    1.00    --   36.47  37.00-120.00   89
  8  \w    -33.00  18.00   1.00    1.00    --   36.47 -77.00 -30.00   51
  9  \w     36.00  65.00   1.00    1.00    --   36.47 -77.00 -30.00   29
 10  \w    -34.00  47.00   1.00    1.00    --   36.47 -37.00  60.00   81
 11  \w     58.00  91.00   1.00    1.00    --   36.47 178.00  90.00   33
 12  \w     68.00  94.00   1.00    1.00    --   36.47 178.00   0.00   26
 13  \w     40.00 100.00   1.00    1.00    --   36.47-140.00-122.00   60
 14  \w    103.00 128.00   1.00    5.50    --  108.00 -45.00 150.00   25
 15  \w     39.00  90.00   1.00    5.50    --  108.00 -45.00 150.00   51
 16  \w     46.00  72.00   1.00    5.50    --  108.00 -61.00 120.00   26
 17  \w     39.00 114.00   1.00    5.50    --  108.00 -45.00 -30.00   75
 18  \w     64.00 169.00   1.00    5.50    --  108.00  15.00-150.00  105
 19  \w     38.00 120.00   1.00    5.50    --  108.00 -45.00  60.00   82
 20  \w     64.00 111.00   1.00    5.50    --  108.00-111.00-150.00   47
 21  \w    120.00 176.00   1.00    5.50    --  108.00  61.00  90.00   56
 22  \w     37.00 111.00   1.00    5.50    --  108.00-111.00 -30.00   74
 23  \w     88.00 121.00   1.00    5.50    --  108.00  45.00   0.00   33
 24  \w    116.00 165.00   1.00    5.50    --  108.00  61.00  30.00   49
 25  \w     46.00 110.00   1.00    5.50    --  108.00 -94.00  90.00   64
 26  \w     61.00 103.00   1.00    5.50    --  108.00-111.00  60.00   42
 27  \w     96.00 153.00   1.00    5.50    --  108.00  45.00 120.00   57
 28  \w     97.00 126.00   1.00    5.50    --  108.00  45.00  90.00   29
 29  \w     69.00 140.00   1.00    5.50    --  108.00 178.00   0.00   71
 30  \w     41.00  85.00   1.00    5.50    --  108.00 -61.00 -60.00   44
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0669125000
_diffrn_orient_matrix_UB_12      -0.0073482000
_diffrn_orient_matrix_UB_13      -0.1214847000
_diffrn_orient_matrix_UB_21      -0.0235141000
_diffrn_orient_matrix_UB_22      -0.1216385000
_diffrn_orient_matrix_UB_23      -0.0151017000
_diffrn_orient_matrix_UB_31      -0.1357816000
_diffrn_orient_matrix_UB_32      0.0049762000
_diffrn_orient_matrix_UB_33      0.0225429000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0401
_diffrn_reflns_av_unetI/netI     0.0539
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            11890
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.062
_diffrn_reflns_theta_max         67.062
_diffrn_reflns_theta_min         3.571
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.802
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81539
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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    1.281
_exptl_crystal_description       prism
_exptl_crystal_F_000             680
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.440
_refine_diff_density_min         -0.471
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     411
_refine_ls_number_reflns         6004
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0934
_refine_ls_R_factor_gt           0.0716
_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^)+(0.1136P)^2^+0.4778P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1933
_refine_ls_wR_factor_ref         0.2204
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4283
_reflns_number_total             6004
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc06777f2.cif
_cod_data_source_block           201909219
_cod_database_code               7127463
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C20H20O4b
_shelx_estimated_absorpt_t_max   0.767
_shelx_estimated_absorpt_t_min   0.578
_reflns_odcompleteness_completeness 99.93
_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. Uiso/Uaniso restraints and constraints
Uanis(Cl2) = Uanis(Cl2A)
Uanis(C34) = Uanis(C34A)
Uanis(Cl1) = Uanis(Cl1A)
Uanis(Cl3) = Uanis(Cl3A)
3. Others
 Sof(C34A)=Sof(H34A)=Sof(Cl1A)=Sof(Cl2A)=1-FVAR(1)
 Sof(C34)=Sof(H34)=Sof(Cl1)=Sof(Cl2)=FVAR(1)
 Sof(Cl3A)=1-FVAR(2)
 Sof(Cl3)=FVAR(2)
4.a Riding coordinates:
 O5(H5a)
4.b Ternary CH refined with riding coordinates:
 C5(H5), C34(H34), C34A(H34A)
4.c Secondary CH2 refined with riding coordinates:
 C12(H12a,H12b)
4.d Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C15(H15), C16(H16), C17(H17), C18(H18),
 C19(H19), C21(H21), C25(H25)
4.e Idealised Me refined as rotating group:
 C13(H13a,H13b,H13c), C27(H27a,H27b,H27c), C28(H28a,H28b,H28c), C29(H29a,H29b,
 H29c), C31(H31a,H31b,H31c), C32(H32a,H32b,H32c), C33(H33a,H33b,H33c)
4.f Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.256
_oxdiff_exptl_absorpt_empirical_full_min 0.847