Formal Oxo- and Aza-[3+2] Reactions of α-Enaminones and Quinones: A Double Divergent Process and the Roles of Chiral Phosphoric Acid and Molecular Sieves
Luo, Weiwei; Sun, Zhicheng; Fernando, E. H. Nisala; Nesterov, Vladimir; Cundari, Thomas R.; Wang, Hong; Chemical Science  (2020) –; doi:10.1039/D0SC02078H

data_1558554
_publ_section_title
;
 Formal Oxo- and Aza-[3+2] Reactions of \a-Enaminones and Quinones: A
 Double Divergent Process and the Roles of Chiral Phosphoric Acid and
 Molecular Sieves
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC02078H
_journal_year                    2020
_chemical_formula_moiety         'C20 H17 N O4'
_chemical_formula_sum            'C20 H17 N O4'
_chemical_formula_weight         335.35
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-02-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-05-28 deposited with the CCDC.	2020-07-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.9840(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   12.27300(10)
_cell_length_b                   13.85930(10)
_cell_length_c                   19.0331(2)
_cell_measurement_reflns_used    21175
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.1770
_cell_measurement_theta_min      3.7150
_cell_volume                     3141.49(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.35a (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_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.985
_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   -121.00 -46.00   0.50    0.50    --  -47.07 -32.00  10.00  150
  2  \w    -41.00  16.00   0.50    0.50    --  -47.07  32.00 169.00  114
  3  \w     53.00  78.00   0.50    0.50    --   47.07  32.00 169.00   50
  4  \w    -25.00   0.00   0.50    0.50    --   47.07 -32.00  10.00   50
  5  \w   -141.00-116.00   0.50    0.50    --  -86.25 -32.00  10.00   50
  6  \w    -47.00 -22.00   0.50    0.50    --  -86.25  32.00 169.00   50
  7  \w     95.00 173.00   0.50    0.50    --  107.75  32.00 169.00  156
  8  \w   -119.00 -79.00   0.50    0.50    --  -47.07-125.00-180.00   80
  9  \w    -27.00  14.00   0.50    0.50    --   47.07 -19.00-150.00   82
 10  \w     85.00 119.00   0.50    0.50    --   47.07  77.00 -30.00   68
 11  \w    -26.00  15.00   0.50    0.50    --   47.07 -19.00 -90.00   82
 12  \w     88.00 118.00   0.50    0.50    --   47.07  77.00-120.00   60
 13  \w    -59.00 -24.00   0.50    0.50    --  -86.25  45.00   0.00   70
 14  \w    -45.00 -20.00   0.50    0.50    --  -86.25  30.00 -30.00   50
 15  \w     34.00  59.00   0.50    0.50    --  107.75 -61.00  90.00   50
 16  \w     54.00  95.00   0.50    0.50    --  107.75 -77.00-150.00   82
 17  \w     34.00  59.00   0.50    0.50    --  107.75 -61.00  60.00   50
 18  \w     34.00  60.00   0.50    0.50    --  107.75 -61.00   0.00   52
 19  \w     60.00  95.00   0.50    0.50    --  107.75 -77.00-120.00   70
 20  \w     34.00  61.00   0.50    0.50    --  107.75 -61.00 -30.00   54
 21  \w     39.00  91.00   0.50    0.50    --  107.75 -77.00  60.00  104
 22  \w     44.00  69.00   0.50    0.50    --  107.75 -77.00  90.00   50
 23  \w     98.00 155.00   0.50    0.50    --  107.75 125.00  60.00  114
 24  \w     37.00  94.00   0.50    0.50    --  107.75 -77.00   0.00  114
 25  \w    105.00 172.00   0.50    0.50    --  107.75 125.00  90.00  134
 26  \w    142.00 177.00   0.50    0.50    --  107.75  45.00 -90.00   70
 27  \w     94.00 135.00   0.50    0.50    --  107.75  45.00 -90.00   82
 28  \w    120.00 173.00   0.50    0.50    --  107.75  15.00  30.00  106
 29  \w     42.00  73.00   0.50    0.50    --  107.75-125.00 -30.00   62
 30  \w     84.00 110.00   0.50    0.50    --  107.75-125.00 -30.00   52
 31  \w     64.00  90.00   0.50    0.50    --  107.75 -77.00  30.00   52
 32  \w     48.00  96.00   0.50    0.50    --  107.75 -77.00 150.00   96
 33  \w     34.00  59.00   0.50    0.50    --  107.75 -61.00  30.00   50
 34  \w     34.00  59.00   0.50    0.50    --  107.75 -61.00 -90.00   50
 35  \w     95.00 145.00   0.50    0.50    --  107.75  45.00-150.00  100
 36  \w     36.00  61.00   0.50    0.50    --  107.75 -61.00-150.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0213243000
_diffrn_orient_matrix_UB_12      -0.0002368000
_diffrn_orient_matrix_UB_13      0.0765087000
_diffrn_orient_matrix_UB_21      0.1161531000
_diffrn_orient_matrix_UB_22      -0.0459255000
_diffrn_orient_matrix_UB_23      0.0301985000
_diffrn_orient_matrix_UB_31      0.0527282000
_diffrn_orient_matrix_UB_32      0.1012546000
_diffrn_orient_matrix_UB_33      0.0138607000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0265
_diffrn_reflns_av_unetI/netI     0.0203
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            29255
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.708
_diffrn_reflns_theta_min         3.712
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.814
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82155
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.35a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.418
_exptl_crystal_description       block
_exptl_crystal_F_000             1408
_exptl_crystal_recrystallization_method 'Vapour deposition'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.319
_refine_diff_density_min         -0.307
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     455
_refine_ls_number_reflns         6612
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0420
_refine_ls_R_factor_gt           0.0392
_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^)+(0.0561P)^2^+1.2199P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1040
_refine_ls_wR_factor_ref         0.1063
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6030
_reflns_number_total             6612
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc02078h2.cif
_cod_data_source_block           str0214lt100kcu
_cod_database_code               1558554
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C20H17NO5
_shelx_estimated_absorpt_t_max   0.968
_shelx_estimated_absorpt_t_min   0.923
_reflns_odcompleteness_completeness 100.00
_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.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C10A(H10C,H10D), C11A(H11C,
 H11D), C12A(H12C,H12D)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C4A(H4A),
 C5A(H5A), C14A(H14A), C15A(H15A), C16A(H16A), C17A(H17A), C18A(H18A)
2.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C20A(H20D,H20E,H20F)
2.d Idealised tetrahedral OH refined as rotating group:
 O2(H2), O2A(H2A)
;
_shelx_res_checksum              56789
_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 1.172
_oxdiff_exptl_absorpt_empirical_full_min 0.840