Diastereodivergent synthesis of 4-oxocyclohexanecarbaldehydes by using the modularly designed organocatalysts upon switching on their iminium catalysis.
Bora, Pranjal; Jakkampudi, Satish; Parella, Ramarao; Sakkani, Nagaraju; Dai, Qipu; Bihani, Manisha; Arman, Hadi D.; Zhao, John C.-G.; Chemical communications (Cambridge, England) 57 (2021) 5334–5337; doi:10.1039/d1cc01020d

data_7128240
_publ_section_title
;
 Diastereodivergent synthesis of 4-oxocyclohexanecarbaldehydes by using
 the modularly designed organocatalysts upon switching on their iminium
 catalysis.
;
_journal_issue                   43
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              5334
_journal_page_last               5337
_journal_paper_doi               10.1039/d1cc01020d
_journal_volume                  57
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H18 N2 O6'
_chemical_formula_sum            'C21 H18 N2 O6'
_chemical_formula_weight         394.37
_chemical_name_systematic
(1R,2R,6S)-2-(4-nitrophenyl)-6-[(E)-4-nitrostyryl]-4-oxocyclohexane-1-carbaldehyde
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-06-17
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.10.09 svn.r3662 for Rigaku Oxford Diffraction, GUI svn.r5959)
;
_audit_update_record
;
2020-11-09 deposited with the CCDC.	2021-04-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.046(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.5200(4)
_cell_length_b                   5.22340(10)
_cell_length_c                   16.8010(3)
_cell_measurement_reflns_used    7833
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.3200
_cell_measurement_theta_min      2.6290
_cell_volume                     1885.89(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT n/a (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.956
_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    -25.00  72.00   0.50    2.80    --   46.75 -80.00  15.00  194
  2  \w     34.00 132.00   0.50   11.20    --  106.69 -80.00  15.00  196
  3  \w     92.00 178.00   0.50   11.20    --  106.69  45.00  90.00  172
  4  \w     83.00 119.00   0.50    2.80    --   46.75  57.00  60.00   72
  5  \w     82.00 178.00   0.50   11.20    --  106.69  80.00 139.00  192
  6  \w     34.00 101.00   0.50   11.20    --  106.69 -77.00 -90.00  134
  7  \w     34.00 101.00   0.50   11.20    --  106.69 -77.00-150.00  134
  8  \w     34.00 111.00   0.50   11.20    --  106.69-125.00-120.00  154
  9  \w     34.00  71.00   0.50   11.20    --  106.69 -61.00  90.00   74
 10  \w     34.00  71.00   0.50   11.20    --  106.69 -61.00 150.00   74
 11  \w     22.00 119.00   0.50    2.80    --   46.75  80.00 139.00  194
 12  \w    -51.00 -16.00   0.50   11.20    --  -88.50  45.00 -30.00   70
 13  \w    -51.00 -16.00   0.50   11.20    --  -88.50  45.00 -90.00   70
 14  \w   -119.00 -21.00   0.50    2.80    --  -46.75 -80.00  15.00  196
 15  \w    -72.00  26.00   0.50    2.80    --  -46.75  80.00 139.00  196
 16  \w   -114.00 -15.00   0.50   11.20    --  -88.50  80.00 139.00  198
 17  \w   -119.00 -83.00   0.50    2.80    --  -46.75 -57.00 -60.00   72
 18  \w   -119.00 -87.00   0.50    2.80    --  -46.75-125.00  60.00   64
 19  \w   -119.00 -87.00   0.50    2.80    --  -46.75-125.00  90.00   64
 20  \w   -160.00 -91.00   0.50   11.20    --  -88.50 -61.00  30.00  138
 21  \w   -160.00 -91.00   0.50   11.20    --  -88.50 -61.00 -90.00  138
 22  \w   -160.00 -63.00   0.50   11.20    --  -88.50 -80.00  15.00  194
 23  \w   -161.00 -74.00   0.50   11.20    --  -88.50 -45.00  60.00  174
 24  \w   -163.00 -73.00   0.50   11.20    --  -88.50 -30.00  90.00  180
 25  \w   -161.00 -74.00   0.50   11.20    --  -88.50 -45.00 -60.00  174
 26  \w   -163.00 -73.00   0.50   11.20    --  -88.50 -30.00-120.00  180
 27  \w   -161.00 -74.00   0.50   11.20    --  -88.50 -45.00-150.00  174
;
_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      -0.0258884000
_diffrn_orient_matrix_UB_12      0.0537048000
_diffrn_orient_matrix_UB_13      0.0820845000
_diffrn_orient_matrix_UB_21      -0.0307778000
_diffrn_orient_matrix_UB_22      0.2472844000
_diffrn_orient_matrix_UB_23      -0.0329871000
_diffrn_orient_matrix_UB_31      -0.0593514000
_diffrn_orient_matrix_UB_32      -0.1514802000
_diffrn_orient_matrix_UB_33      -0.0246216000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0587
_diffrn_reflns_av_unetI/netI     0.0434
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            13035
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.904
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.432
_diffrn_reflns_theta_min         2.634
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.863
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.637
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.63a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.389
_exptl_crystal_description       needle
_exptl_crystal_F_000             824
_exptl_crystal_size_max          0.196
_exptl_crystal_size_mid          0.105
_exptl_crystal_size_min          0.046
_refine_diff_density_max         0.319
_refine_diff_density_min         -0.286
_refine_diff_density_rms         0.076
_refine_ls_abs_structure_details
;
 Flack x determined using 1314 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.05(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     262
_refine_ls_number_reflns         3580
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0664
_refine_ls_R_factor_gt           0.0553
_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^)+(0.0550P)^2^+4.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1343
_refine_ls_wR_factor_ref         0.1373
_reflns_Friedel_coverage         0.699
_reflns_Friedel_fraction_full    0.956
_reflns_Friedel_fraction_max     0.840
_reflns_number_gt                3391
_reflns_number_total             3580
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc01020d2.cif
_cod_data_source_block           hpd122
_cod_depositor_comments
'Adding full bibliography for 7128238--7128240.cif.'
_cod_database_code               7128240
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O'
_chemical_oxdiff_usercomment     Pure1-RP-2120
_shelx_estimated_absorpt_t_max   0.961
_shelx_estimated_absorpt_t_min   0.849
_reflns_odcompleteness_completeness 99.95
_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
2.a Ternary CH refined with riding coordinates:
 C6(H6), C1(H1), C2(H2)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C3(H3A,H3B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C17(H17), C8(H8), C12(H12), C14(H14), C20(H20), C18(H18), C9(H9),
 C15(H15), C11(H11), C21(H21)
;
_olex2_exptl_crystal_mounting_method 'nylon loop'
_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 1.889
_oxdiff_exptl_absorpt_empirical_full_min 0.563