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_1558553
_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 rmad
_chemical_formula_moiety         'C14 H14 O6'
_chemical_formula_sum            'C14 H14 O6'
_chemical_formula_weight         278.25
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-04
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.01.05 svn.r3372 for Rigaku Oxford Diffraction, GUI svn.r5289)
;
_audit_update_record
;
2019-06-05 deposited with the CCDC.	2020-07-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   7.17307(3)
_cell_length_b                   9.46902(5)
_cell_length_c                   36.9162(2)
_cell_measurement_reflns_used    37812
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.4330
_cell_measurement_theta_min      3.6050
_cell_volume                     2507.42(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    '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 1.000
_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     11.00 116.00   0.50    0.50    --   39.20  57.00  60.00  210
  2  \w    102.00 178.00   0.50    0.50    --  116.00 104.00 140.00  152
  3  \w     99.00 178.00   0.50    0.50    --  116.00 111.00 120.00  158
  4  \w     85.00 178.00   0.50    0.50    --  116.00  77.00  30.00  186
  5  \w     99.00 178.00   0.50    0.50    --  116.00 111.00-120.00  158
  6  \w     99.00 178.00   0.50    0.50    --  116.00 111.00-180.00  158
  7  \w     99.00 178.00   0.50    0.50    --  116.00 111.00-150.00  158
  8  \w     85.00 178.00   0.50    0.50    --  116.00  77.00-150.00  186
  9  \w     86.00 178.00   0.50    0.50    --  116.00  45.00 -90.00  184
 10  \w     86.00 178.00   0.50    0.50    --  116.00  61.00  90.00  184
 11  \w     78.00 178.00   0.50    0.50    --  116.00  30.00-120.00  200
 12  \w     86.00 178.00   0.50    0.50    --  116.00  45.00-180.00  184
 13  \w     85.00 178.00   0.50    0.50    --  116.00  77.00-180.00  186
 14  \w     59.00 150.00   0.50    0.50    --  116.00 178.00 -90.00  182
 15  \w     59.00 150.00   0.50    0.50    --  116.00 178.00  60.00  182
 16  \w     35.00 178.00   0.50    0.50    --  116.00  15.00  30.00  286
 17  \w     35.00 111.00   0.50    0.50    --  116.00-104.00  39.00  152
 18  \w     41.00  96.00   0.50    0.50    --  116.00 -77.00  60.00  110
 19  \w     35.00 109.00   0.50    0.50    --  116.00 -94.00 150.00  148
 20  \w     35.00 112.00   0.50    0.50    --  116.00-111.00  90.00  154
 21  \w     35.00 112.00   0.50    0.50    --  116.00-111.00   0.00  154
 22  \w     30.00 100.00   0.50    0.50    --   39.20-125.00 -90.00  140
 23  \w     41.00  96.00   0.50    0.50    --  116.00 -77.00-150.00  110
 24  \w     41.00  96.00   0.50    0.50    --  116.00 -77.00-180.00  110
 25  \w     35.00 112.00   0.50    0.50    --  116.00-111.00-120.00  154
 26  \w     35.00 109.00   0.50    0.50    --  116.00 -94.00-120.00  148
 27  \w     35.00 112.00   0.50    0.50    --  116.00-111.00 -30.00  154
 28  \w     35.00 109.00   0.50    0.50    --  116.00 -94.00-180.00  148
 29  \w     35.00 112.00   0.50    0.50    --  116.00-111.00 -60.00  154
 30  \w     35.00 109.00   0.50    0.50    --  116.00 -94.00  60.00  148
 31  \w     35.00 112.00   0.50    0.50    --  116.00-111.00 150.00  154
 32  \w     13.00  88.00   0.50    0.50    --   39.20-104.00  39.00  150
 33  \w     11.00 116.00   0.50    0.50    --   39.20  57.00-180.00  210
 34  \w      4.00  41.00   0.50    0.50    --   39.20  77.00-120.00   74
 35  \w      4.00  41.00   0.50    0.50    --   39.20  77.00-180.00   74
 36  \w      4.00  41.00   0.50    0.50    --   39.20  77.00 -90.00   74
 37  \w      4.00  41.00   0.50    0.50    --   39.20  77.00 -30.00   74
 38  \w      4.00  41.00   0.50    0.50    --   39.20  77.00   0.00   74
 39  \w      4.00  41.00   0.50    0.50    --   39.20  77.00  60.00   74
 40  \w      4.00  41.00   0.50    0.50    --   39.20  77.00  30.00   74
 41  \w      4.00  41.00   0.50    0.50    --   39.20  77.00  90.00   74
 42  \w      4.00  41.00   0.50    0.50    --   39.20  77.00 150.00   74
 43  \w    -46.00  16.00   0.50    0.50    --   39.20 -19.00  60.00  124
 44  \w    -46.00  16.00   0.50    0.50    --   39.20 -19.00  30.00  124
 45  \w    -46.00  16.00   0.50    0.50    --   39.20 -19.00  90.00  124
 46  \w    -67.00  37.00   0.50    0.50    --  -39.20  57.00  30.00  208
 47  \w    -45.00 -11.00   0.50    0.50    --  -94.50  30.00 -30.00   68
 48  \w    -45.00 -11.00   0.50    0.50    --  -94.50  30.00   0.00   68
 49  \w    -45.00 -11.00   0.50    0.50    --  -94.50  30.00 -90.00   68
 50  \w    -45.00 -11.00   0.50    0.50    --  -94.50  30.00-180.00   68
 51  \w   -118.00 -78.00   0.50    0.50    --  -39.20-125.00-150.00   80
 52  \w   -118.00 -78.00   0.50    0.50    --  -39.20-125.00-180.00   80
 53  \w   -176.00 -80.00   0.50    0.50    --  -94.50-104.00  39.00  192
 54  \w   -118.00 -78.00   0.50    0.50    --  -39.20-125.00  90.00   80
 55  \w   -171.00 -64.00   0.50    0.50    --  -94.50 -61.00 120.00  214
 56  \w    -45.00 -11.00   0.50    0.50    --  -94.50  30.00 150.00   68
 57  \w    -45.00 -11.00   0.50    0.50    --  -94.50  30.00 120.00   68
 58  \w    -86.00   8.00   0.50    0.50    --  -39.20 104.00 140.00  188
 59  \w      4.00  41.00   0.50    0.50    --   39.20  77.00 -60.00   74
 60  \w    -85.00 -13.00   0.50    0.50    --  -94.50 104.00 140.00  144
;
_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      -0.0168024000
_diffrn_orient_matrix_UB_12      -0.0008488000
_diffrn_orient_matrix_UB_13      0.0416136000
_diffrn_orient_matrix_UB_21      0.0584828000
_diffrn_orient_matrix_UB_22      -0.1565022000
_diffrn_orient_matrix_UB_23      0.0006755000
_diffrn_orient_matrix_UB_31      0.2059133000
_diffrn_orient_matrix_UB_32      0.0444454000
_diffrn_orient_matrix_UB_33      0.0032064000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0357
_diffrn_reflns_av_unetI/netI     0.0134
_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       -7
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            52023
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.474
_diffrn_reflns_theta_min         4.792
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.986
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84005
_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            'clear light colourless'
_exptl_crystal_density_diffrn    1.474
_exptl_crystal_description       block
_exptl_crystal_F_000             1168
_exptl_crystal_recrystallization_method 'Vapour deposition'
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.035
_refine_diff_density_max         0.848
_refine_diff_density_min         -0.347
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 2120 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(3)
_refine_ls_extinction_coef       0.00095(17)
_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   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     369
_refine_ls_number_reflns         5118
_refine_ls_number_restraints     39
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0314
_refine_ls_R_factor_gt           0.0311
_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^)+(0.0427P)^2^+0.8631P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0804
_refine_ls_wR_factor_ref         0.0806
_reflns_Friedel_coverage         0.731
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                5059
_reflns_number_total             5118
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc02078h2.cif
_cod_data_source_block           str0268lt100kcu
_cod_database_code               1558553
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C14H10O6
_diffrn_oxdiff_ac3_digest_frames
;
01fa6e92c5b04c14b45882ea8dceb65f8e000578c83
;
_diffrn_oxdiff_ac3_digest_hkl
;
013fa937a9e11914ff5eedb4a72c19eba11306
;
_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, All C(H,H,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(C4A) = Uanis(C5A) = Uanis(C4B) = Uanis(C5B)
3. Rigid body (RIGU) restrains
 C6A, C5A, C4A, C3A, C2A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C6A, C5B, C4B, C3A, C2A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Others
 Sof(H3AC)=Sof(H3AD)=Sof(H6AB)=Sof(C4B)=Sof(H4BA)=Sof(H4BB)=Sof(C5B)=Sof(H5BA)=
 Sof(H5BB)=1-FVAR(1)
 Sof(H3AA)=Sof(H3AB)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=
 Sof(H6AA)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C6A(H6AA), C6A(H6AB), C6(H6B)
5.b Secondary CH2 refined with riding coordinates:
 C3A(H3AA,H3AB), C3A(H3AC,H3AD), C4A(H4AA,H4AB), C5A(H5AA,H5AB), C3(H3A,H3B),
 C4(H4A,H4B), C5(H5A,H5B), C4B(H4BA,H4BB), C5B(H5BA,H5BB)
5.c Aromatic/amide H refined with riding coordinates:
 C10A(H10A), C11A(H11A), C10(H10), C11(H11)
5.d Idealised Me refined as rotating group:
 C14A(H14A,H14B,H14C), C14(H14D,H14E,H14F)
5.e Idealised tetrahedral OH refined as rotating group:
 O2A(H2A), O6A(H6A), O2(H2), O6(H6)
;
_shelx_res_checksum              20208
_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 1.311
_oxdiff_exptl_absorpt_empirical_full_min 0.797