Organocatalyzed Kinetic Resolution of α-Functionalized Ketones: The Malonate Unit Leads the Way
Liu, Jian; Vasamsetty, Laxmaiah; Anwar, Muhammad; Yang, Shuang; Xu, Weici; Liu, Jinggong; Nagaraju, Sakkani; Fang, Xinqiang; ACS Catalysis  (2020) 2882–2893; doi:10.1021/acscatal.9b05608

data_4517424
_publ_section_title
;
 Organocatalyzed Kinetic Resolution of \a-Functionalized Ketones: The
 Malonate Unit Leads the Way
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              2882
_journal_page_last               2893
_journal_paper_doi               10.1021/acscatal.9b05608
_journal_year                    2020
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C23 H24 O4'
_chemical_formula_sum            'C23 H24 O4'
_chemical_formula_weight         364.44
_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'
_symmetry_Int_Tables_number      4
_audit_creation_date             2018-09-15
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.369(1)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.4234(1)
_cell_length_b                   6.0234(1)
_cell_length_c                   15.0661(1)
_cell_measurement_reflns_used    15643
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.7160
_cell_measurement_theta_min      2.9270
_cell_volume                     945.895(19)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.9697
_diffrn_measured_fraction_theta_max 0.9697
_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    -23.00  17.00   0.50    0.50    --    0.00 -38.00 150.00   80
  2  \w    -77.00 -34.00   0.50    0.50    --    0.00 -38.00 150.00   86
  3  \w     -2.00  51.00   0.50    0.50    --   28.00  79.00 -25.05  106
  4  \w      4.00  31.00   0.50    0.50    --   32.00  74.00 122.16   54
  5  \w     82.00 112.00   0.50    0.50    --   32.00  74.00 122.16   60
  6  \w      9.00  72.00   0.50    0.50    --   40.00  82.00 174.14  126
  7  \w     30.00  87.00   0.50    0.50    --   48.00  78.00  67.06  114
  8  \w     29.00  54.00   0.50    0.50    --   60.00  82.00-100.49   50
  9  \w    119.00 145.00   0.50    0.50    --   60.00  81.00 165.56   52
 10  \w     29.00  55.00   0.50    0.50    --   60.00  81.00 165.56   52
 11  \w     33.00  70.00   0.50    0.50    --   64.00  82.00  11.51   74
 12  \w     39.00  64.00   0.50    0.50    --   68.00  82.00  85.21   50
 13  \w    113.00 157.00   0.50    0.50    --   68.00  82.00  85.21   88
 14  \w     38.00  79.00   0.50    0.50    --   68.00  80.00 -43.81   82
 15  \w     38.00  65.00   0.50    0.50    --   68.00  81.00-165.43   54
 16  \w     49.00  75.00   0.50    0.50    --   72.00  82.00  23.56   52
 17  \w     42.00  77.00   0.50    0.50    --   72.00  81.00-154.50   70
 18  \w     41.00  72.00   0.50    0.50    --   72.00  82.00 -78.83   62
 19  \w     91.00 117.00   0.50    0.50    --   72.00  82.00  95.77   52
 20  \w    102.00 161.00   0.50    0.50    --   72.00  82.00 -78.83  118
 21  \w     41.00  74.00   0.50    0.50    --   72.00  82.00  95.77   66
 22  \w     90.00 116.00   0.50    0.50    --   76.00  76.00-100.64   52
 23  \w     47.00  73.00   0.50    0.50    --   76.00  76.00-100.64   52
 24  \w    137.00 169.00   0.50    0.50    --   80.00  81.00   3.04   64
 25  \w     50.00  77.00   0.50    0.50    --   80.00  81.00   3.04   54
 26  \w    104.00 168.00   0.50    0.50    --   80.00  74.00 141.76  128
 27  \w     52.00  78.00   0.50    0.50    --   80.00  74.00 141.76   52
 28  \w     49.00 164.00   0.50    0.50    --   80.00  82.00 -37.44  230
 29  \w    120.00 185.00   0.50    0.50    --   95.20  77.00  60.00  130
 30  \w     68.00  96.00   0.50    0.50    --   95.20  77.00  60.00   56
 31  \w    104.00 185.00   0.50    0.50    --   95.20  63.00-137.16  162
 32  \w     67.00 185.00   0.50    0.50    --   95.20  82.00 -30.00  236
 33  \w    160.00 185.00   0.50    0.50    --   95.20  82.00 -90.00   50
 34  \w     72.00 100.00   0.50    0.50    --   95.20  63.00-137.16   56
 35  \w     64.00 145.00   0.50    0.50    --   95.20  82.00 -90.00  162
 36  \w      8.00  68.00   0.50    0.50    --   95.20 -61.00 -30.00  120
 37  \w     73.00 134.00   0.50    0.50    --   95.20  61.00-120.00  122
 38  \w     64.00 172.00   0.50    0.50    --   95.20  82.00  90.00  216
 39  \w      7.00 123.00   0.50    0.50    --   95.20 -77.00  30.00  232
 40  \w     60.00 126.00   0.50    0.50    --   95.20 -82.00-180.00  132
 41  \w     96.00 122.00   0.50    0.50    --   95.20 -82.00 -30.00   52
 42  \w     62.00 127.00   0.50    0.50    --   95.20 -82.00 -90.00  130
 43  \w     51.00  76.00   0.50    0.50    --   95.20 -82.00 -30.00   50
 44  \w     83.00 130.00   0.50    0.50    --   95.20  30.00 -30.00   94
 45  \w     73.00 166.00   0.50    0.50    --   95.20  61.00  30.00  186
 46  \w     56.00 113.00   0.50    0.50    --   95.20 -82.00  90.00  114
 47  \w     66.00 117.00   0.50    0.50    --   95.20  82.00 120.00  102
 48  \w    160.00 185.00   0.50    0.50    --   95.20  82.00-120.00   50
 49  \w     64.00 141.00   0.50    0.50    --   95.20  82.00-120.00  154
 50  \w     81.00 115.00   0.50    0.50    --   95.20 -61.00 150.00   68
 51  \w      6.00  21.50   0.50    0.50    --   95.20 -61.00 150.00   31
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1246627000
_diffrn_orient_matrix_UB_12      0.0595423000
_diffrn_orient_matrix_UB_13      -0.0500856000
_diffrn_orient_matrix_UB_21      0.0509629000
_diffrn_orient_matrix_UB_22      -0.1168277000
_diffrn_orient_matrix_UB_23      -0.0836292000
_diffrn_orient_matrix_UB_31      -0.0608610000
_diffrn_orient_matrix_UB_32      -0.2195938000
_diffrn_orient_matrix_UB_33      0.0309054000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0452
_diffrn_reflns_av_unetI/netI     0.0265
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            18965
_diffrn_reflns_theta_full        74.0510
_diffrn_reflns_theta_max         74.05
_diffrn_reflns_theta_min         2.93
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.698
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42922
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
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    1.2795
_exptl_crystal_description       plate
_exptl_crystal_F_000             389.2593
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.1331
_refine_diff_density_min         -0.1744
_refine_diff_density_rms         0.0445
_refine_ls_abs_structure_details
'Flack, H. D. (1983). Acta Cryst. A39, 876-881.'
_refine_ls_abs_structure_Flack   -0.05(11)
_refine_ls_d_res_high            0.8018
_refine_ls_d_res_low             15.0658
_refine_ls_goodness_of_fit_ref   1.0697
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    41
_refine_ls_number_parameters     246
_refine_ls_number_reflns         3713
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0697
_refine_ls_R_factor_all          0.0325
_refine_ls_R_factor_gt           0.0321
_refine_ls_shift/su_max          0.0000
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0500P)^2^+0.1266P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0838
_refine_ls_wR_factor_ref         0.0841
_reflns_Friedel_coverage         0.947
_reflns_limit_h_max              13
_reflns_limit_h_min              -12
_reflns_limit_k_max              7
_reflns_limit_k_min              -7
_reflns_limit_l_max              18
_reflns_limit_l_min              -18
_reflns_number_gt                3648
_reflns_number_total             3713
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            cs9b05608_si_004.cif
_cod_data_source_block           20180915-2
_cod_depositor_comments
'Adding full bibliography for 4517422--4517424.cif.'
_cod_original_sg_symbol_Hall     ' P 2yb'
_cod_database_code               4517424
_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
2.a Ternary CH refined with riding coordinates:
 C9(H9), C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C11(H11a,H11b)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C5(H5), C6(H6), C8(H8), C15(H15), C16(H16), C17(H17),
 C18(H18), C19(H19)
2.d Idealised Me refined as rotating group:
 C13(H13a,H13b,H13c), C20(H20a,H20b,H20c), C23(H23a,H23b,H23c)
;
_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 1.668
_oxdiff_exptl_absorpt_empirical_full_min 0.286