Asymmetric Cycloaddition of ortho-Hydroxyphenyl-Substituted para-Quinone Methides and Enamides Catalyzed by Chiral Phosphoric Acid.
Yang, Guo-Hui; Zhao, Qun; Zhang, Zhi-Pei; Zheng, Han-Liang; Chen, Li; Li, Xin; The Journal of organic chemistry 84 (2019) 7883–7893; doi:10.1021/acs.joc.9b00749

data_4034650
_publ_section_title
;
 Asymmetric Cycloaddition of ortho-Hydroxyphenyl-Substituted para-Quinone
 Methides and Enamides Catalyzed by Chiral Phosphoric Acid.
;
_journal_issue                   12
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              7883
_journal_page_last               7893
_journal_paper_doi               10.1021/acs.joc.9b00749
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C33 H39 N O3'
_chemical_formula_sum            'C33 H39 N O3'
_chemical_formula_weight         497.65
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.12340(10)
_cell_length_b                   16.34880(10)
_cell_length_c                   37.5189(3)
_cell_measurement_reflns_used    33163
_cell_measurement_temperature    295.15
_cell_measurement_theta_max      78.7520
_cell_measurement_theta_min      2.3990
_cell_volume                     5596.19(8)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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_temperature      295.15
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.990
_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   -138.00  15.00   0.50    6.00    --  -49.50 -17.00 121.00  306
  2  \w   -199.00 -45.00   0.50   24.00    -- -110.00 -17.00 121.00  308
  3  \w    -82.00  39.00   0.50    6.00    --  -49.50  70.00 -51.40  242
  4  \w   -138.00 -16.00   0.50    6.00    --  -49.50 -72.00  30.00  244
  5  \w   -140.00 -21.00   0.50   24.00    -- -110.00  57.00 120.00  238
  6  \w   -144.00 -21.00   0.50   24.00    -- -110.00  72.00 120.00  246
  7  \w   -199.00 -76.00   0.50   24.00    -- -110.00 -72.00-142.58  246
  8  \w   -199.00 -80.00   0.50   24.00    -- -110.00 -47.00  20.10  238
  9  \w   -199.00 -80.00   0.50   24.00    -- -110.00 -47.00  20.10  238
 10  \w   -144.00 -21.00   0.50   24.00    -- -110.00  72.00   0.00  246
 11  \w   -199.00 -80.00   0.50   24.00    -- -110.00 -48.00 131.33  238
 12  \w   -144.00 -21.00   0.50   24.00    -- -110.00  72.00  90.00  246
 13  \w   -197.00 -81.00   0.50   24.00    -- -110.00 -57.00-150.00  232
 14  \w   -177.00-151.00   0.50   24.00    -- -110.00 -57.00-180.00   52
 15  \w   -131.00-105.00   0.50   24.00    -- -110.00 -57.00-180.00   52
 16  \w   -103.00 -77.00   0.50   24.00    -- -110.00  17.00 -68.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RCD3): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0332364000
_diffrn_orient_matrix_UB_12      0.0653677000
_diffrn_orient_matrix_UB_13      0.0284455000
_diffrn_orient_matrix_UB_21      0.0163493000
_diffrn_orient_matrix_UB_22      -0.0675734000
_diffrn_orient_matrix_UB_23      0.0283454000
_diffrn_orient_matrix_UB_31      0.1647205000
_diffrn_orient_matrix_UB_32      -0.0064823000
_diffrn_orient_matrix_UB_33      -0.0085757000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0384
_diffrn_reflns_av_unetI/netI     0.0260
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            67385
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.209
_diffrn_reflns_theta_min         2.355
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.583
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64756
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.181
_exptl_crystal_description       needle
_exptl_crystal_F_000             2144
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.189
_refine_diff_density_min         -0.116
_refine_diff_density_rms         0.031
_refine_ls_abs_structure_details
;
 Flack x determined using 4625 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.17(7)
_refine_ls_extinction_coef       0.00084(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     698
_refine_ls_number_reflns         11940
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0382
_refine_ls_R_factor_gt           0.0355
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0534P)^2^+0.4717P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0937
_refine_ls_wR_factor_ref         0.0958
_reflns_Friedel_coverage         0.786
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.976
_reflns_number_gt                11135
_reflns_number_total             11940
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00749_si_002.cif
_cod_data_source_block           p20180705b
_cod_database_code               4034650
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C33H47NO3
_shelx_estimated_absorpt_t_max   0.966
_shelx_estimated_absorpt_t_min   0.818
_reflns_odcompleteness_completeness 99.53
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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. Restrained distances
 H4-H47A
 2.1 with sigma of 0.005
 O1-H1
 0.85 with sigma of 0.005
 H12C-H1
 2.1 with sigma of 0.005
3.a Ternary CH refined with riding coordinates:
 C15(H15), C16(H16), C48(H48), C49(H49)
3.b Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C25(H25A,H25B), C57(H57A,H57B), C58(H58A,H58B)
3.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C19(H19), C20(H20), C21(H21), C22(H22), C28(H28), C29(H29),
 C30(H30), C31(H31), C36(H36), C38(H38), C52(H52), C53(H53), C54(H54), C55(H55),
  C61(H61), C62(H62), C63(H63), C64(H64)
3.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C33(H33A,H33B,H33C), C41(H41A,H41B,
 H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C45(H45A,H45B,H45C), C46(H46A,
 H46B,H46C), C47(H47A,H47B,H47C), C66(H66A,H66B,H66C)
;
_shelx_res_checksum              81975
_shelx_hkl_checksum              38639
_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 1.723
_oxdiff_exptl_absorpt_empirical_full_min 0.540