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_4517423
_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_formula_moiety         'C23 H24 O5'
_chemical_formula_sum            'C23 H24 O5'
_chemical_formula_weight         380.42
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-05-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.03 svn.r3497 for OlexSys, GUI svn.r5486)
;
_cell_angle_alpha                81.344(3)
_cell_angle_beta                 79.625(3)
_cell_angle_gamma                70.309(4)
_cell_formula_units_Z            4
_cell_length_a                   8.4862(4)
_cell_length_b                   11.6076(5)
_cell_length_c                   21.8095(8)
_cell_measurement_reflns_used    8410
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      27.8570
_cell_measurement_theta_min      2.5920
_cell_volume                     1980.25(15)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3468
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  91.00   1.00   14.40    --   11.14  77.00 -60.00  116
  2  \w    -20.00  31.00   1.00   14.40    --   11.14 -99.00 150.00   51
  3  \w    -46.00  42.00   1.00   14.40    --   11.14 -38.00   0.00   88
  4  \w     -1.00  90.00   1.00   14.40    --   11.14  38.00-180.00   91
  5  \w     47.00 104.00   1.00   14.40    --   11.14 178.00 -60.00   57
  6  \w    -12.00  85.00   1.00   14.40    --   11.14  38.00  90.00   97
  7  \w    -53.00  10.00   1.00   14.40    --  -12.00  90.00 -73.57   63
  8  \w    -73.00 -41.00   1.00   14.40    --  -12.00 127.00  80.28   32
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0502602000
_diffrn_orient_matrix_UB_12      0.0372203000
_diffrn_orient_matrix_UB_13      -0.0145070000
_diffrn_orient_matrix_UB_21      -0.0629085000
_diffrn_orient_matrix_UB_22      0.0523739000
_diffrn_orient_matrix_UB_23      0.0121031000
_diffrn_orient_matrix_UB_31      0.0394009000
_diffrn_orient_matrix_UB_32      -0.0111272000
_diffrn_orient_matrix_UB_33      0.0273242000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0363
_diffrn_reflns_av_unetI/netI     0.0362
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            25295
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         1.872
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.089
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74162
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.276
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             808
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.207
_refine_diff_density_min         -0.224
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     511
_refine_ls_number_reflns         6952
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0603
_refine_ls_R_factor_gt           0.0433
_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^)+(0.0540P)^2^+0.4045P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1089
_refine_ls_wR_factor_ref         0.1164
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5343
_reflns_number_total             6952
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b05608_si_002.cif
_cod_data_source_block           lxx-0531
_cod_depositor_comments
;

2020-04-01
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel

 Adding full bibliography for 4517422--4517424.cif.
;
_cod_original_cell_volume        1980.27(15)
_cod_original_formula_moiety     '2(C23 H24 O5)'
_cod_original_formula_sum        'C46 H48 O10'
_cod_original_formula_units_Z    2
_cod_original_formula_weight     760.84
_cod_database_code               4517423
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C H O'
_reflns_odcompleteness_completeness 96.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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:
 C33(H33), C5(H5), C30(H30), C2(H2)
2.b Secondary CH2 refined with riding coordinates:
 C31(H31A,H31B), C3(H3A,H3B)
2.c Aromatic/amide H refined with riding coordinates:
 C34(H34), C8(H8), C36(H36), C40(H40), C42(H42), C44(H44), C6(H6), C45(H45),
 C18(H18), C46(H46), C43(H43), C14(H14), C37(H37), C39(H39), C16(H16), C12(H12),
  C17(H17), C9(H9), C15(H15), C10(H10), C38(H38), C11(H11)
2.d Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C56(H56A,H56B,H56C), C53(H53A,H53B,H53C), C49(H49A,H49B,
 H49C), C28(H28A,H28B,H28C), C21(H21A,H21B,H21C)
;
_shelx_res_checksum              70775
_shelx_hkl_checksum              96782
_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 1.564
_oxdiff_exptl_absorpt_empirical_full_min 0.629