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_1558552
_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_absolute_configuration ad
_chemical_formula_moiety         'C20 H19 N O5'
_chemical_formula_sum            'C20 H19 N O5'
_chemical_formula_weight         353.36
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-02-15
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.01.05 svn.r3372 for Rigaku Oxford Diffraction, GUI svn.r5289)
;
_audit_update_record
;
2019-05-28 deposited with the CCDC.	2020-07-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.4510(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.94010(10)
_cell_length_b                   10.34330(10)
_cell_length_c                   9.39150(10)
_cell_measurement_reflns_used    23615
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.5150
_cell_measurement_theta_min      4.2890
_cell_volume                     844.611(16)
_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 0.994
_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    -26.00  35.00   0.50    1.00    --   47.20 -40.00 -35.00  122
  2  \w     31.00 121.00   0.50    1.00    --   47.20  57.00-120.00  180
  3  \w     90.00 178.00   0.50    0.50    --  107.75  61.00-180.00  176
  4  \w     93.00 178.00   0.50    0.50    --  107.75  15.00-150.00  170
  5  \w     90.00 178.00   0.50    0.50    --  107.75  61.00 -90.00  176
  6  \w     94.00 178.00   0.50    0.50    --  107.75  45.00-120.00  168
  7  \w     94.00 178.00   0.50    0.50    --  107.75  45.00 -90.00  168
  8  \w     85.00 178.00   0.50    0.50    --  107.75  77.00   0.00  186
  9  \w     94.00 178.00   0.50    0.50    --  107.75  40.00 118.00  168
 10  \w     93.00 178.00   0.50    0.50    --  107.75  15.00   0.00  170
 11  \w     90.00 178.00   0.50    0.50    --  107.75  61.00-120.00  176
 12  \w     85.00 178.00   0.50    0.50    --  107.75  77.00-120.00  186
 13  \w     85.00 178.00   0.50    0.50    --  107.75  77.00-150.00  186
 14  \w     90.00 178.00   0.50    0.50    --  107.75  61.00-150.00  176
 15  \w     85.00 178.00   0.50    0.50    --  107.75  77.00-180.00  186
 16  \w     31.00 121.00   0.50    1.00    --   47.20  57.00-180.00  180
 17  \w     34.00  61.00   0.50    0.50    --  107.75 -61.00 -30.00   54
 18  \w     34.00  96.00   0.50    0.50    --  107.75 -77.00  30.00  124
 19  \w     34.00  96.00   0.50    0.50    --  107.75 -77.00 150.00  124
 20  \w     34.00  96.00   0.50    0.50    --  107.75 -77.00  90.00  124
 21  \w     34.00  96.00   0.50    0.50    --  107.75 -77.00   0.00  124
 22  \w     34.00  61.00   0.50    0.50    --  107.75 -61.00 120.00   54
 23  \w     34.00  61.00   0.50    0.50    --  107.75 -61.00  60.00   54
 24  \w     34.00  96.00   0.50    0.50    --  107.75 -77.00  60.00  124
 25  \w     34.00 117.00   0.50    0.50    --  107.75-125.00   0.00  166
 26  \w     34.00  96.00   0.50    0.50    --  107.75 -77.00-150.00  124
 27  \w     34.00 109.00   0.50    0.50    --  107.75 -94.00 -30.00  150
 28  \w     34.00  96.00   0.50    0.50    --  107.75 -77.00-120.00  124
 29  \w     34.00  61.00   0.50    0.50    --  107.75 -61.00-180.00   54
 30  \w     30.00  96.00   0.50    1.00    --   47.20-125.00-180.00  132
 31  \w     30.00 120.00   0.50    1.00    --   47.20  60.00 -34.30  180
 32  \w     34.00 121.00   0.50    1.00    --   47.20  40.00 118.00  174
 33  \w     90.00 178.00   0.50    0.50    --  107.75  61.00 150.00  176
 34  \w     85.00 178.00   0.50    0.50    --  107.75  77.00 150.00  186
 35  \w     34.00  61.00   0.50    0.50    --  107.75 -61.00 150.00   54
 36  \w     31.00 121.00   0.50    1.00    --   47.20  57.00  90.00  180
 37  \w     31.00 121.00   0.50    1.00    --   47.20  57.00 -60.00  180
 38  \w     27.00 121.00   0.50    1.00    --   47.20  69.00   3.56  188
 39  \w    -55.00 -13.00   0.50    0.50    --  -86.25  40.00 118.00   84
 40  \w    -55.00  26.00   0.50    1.00    --  -47.20  40.00 118.00  162
 41  \w    -92.00 -13.00   0.50    0.50    --  -86.25 125.00 150.00  158
 42  \w   -121.00 -33.00   0.50    1.00    --  -47.20 -40.00 -35.00  176
 43  \w   -121.00 -85.00   0.50    1.00    --  -47.20 -77.00-120.00   72
 44  \w   -160.00 -72.00   0.50    0.50    --  -86.25 -40.00 -35.00  176
 45  \w   -121.00 -31.00   0.50    1.00    --  -47.20 -57.00  60.00  180
 46  \w   -121.00 -78.00   0.50    1.00    --  -47.20-125.00 120.00   86
 47  \w   -121.00 -31.00   0.50    1.00    --  -47.20 -57.00 120.00  180
 48  \w   -160.00 -67.00   0.50    0.50    --  -86.25 -65.00-134.40  186
 49  \w   -160.00 -67.00   0.50    0.50    --  -86.25 -65.00-167.73  186
 50  \w   -160.00 -71.00   0.50    0.50    --  -86.25 -56.00-162.83  178
 51  \w   -160.00 -68.00   0.50    0.50    --  -86.25 -63.00 -97.97  184
 52  \w   -160.00 -70.00   0.50    0.50    --  -86.25 -59.00-127.64  180
 53  \w   -160.00 -71.00   0.50    0.50    --  -86.25 -54.00 162.48  178
 54  \w   -160.00 -69.00   0.50    0.50    --  -86.25 -61.00 150.00  182
;
_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      -0.0250149000
_diffrn_orient_matrix_UB_12      -0.0566710000
_diffrn_orient_matrix_UB_13      -0.1554979000
_diffrn_orient_matrix_UB_21      -0.1594413000
_diffrn_orient_matrix_UB_22      -0.0499868000
_diffrn_orient_matrix_UB_23      0.0103931000
_diffrn_orient_matrix_UB_31      -0.0730674000
_diffrn_orient_matrix_UB_32      0.1283451000
_diffrn_orient_matrix_UB_33      -0.0645514000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0204
_diffrn_reflns_av_unetI/netI     0.0095
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            24355
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.758
_diffrn_reflns_theta_min         4.842
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.830
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89379
_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    1.389
_exptl_crystal_description       block
_exptl_crystal_F_000             372
_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         0.156
_refine_diff_density_min         -0.184
_refine_diff_density_rms         0.041
_refine_ls_abs_structure_details
;
 Flack x determined using 1632 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     237
_refine_ls_number_reflns         3535
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0257
_refine_ls_R_factor_gt           0.0257
_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^)+(0.0405P)^2^+0.1436P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0666
_refine_ls_wR_factor_ref         0.0666
_reflns_Friedel_coverage         0.869
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.969
_reflns_number_gt                3523
_reflns_number_total             3535
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc02078h2.cif
_cod_data_source_block           str0216lt100kcu
_cod_database_code               1558552
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C20H19NO5
_diffrn_oxdiff_ac3_digest_frames
;
01a498c46c2aae4cac3c71311375d44f600003231a7
;
_diffrn_oxdiff_ac3_digest_hkl
;
012a8fe14af72073b8257c4491dc3bf67fe49d
;
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C2(H2A), C3(H3), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18)
2.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C)
2.e Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_shelx_res_checksum              68345
_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 1.214
_oxdiff_exptl_absorpt_empirical_full_min 0.876