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_4517422
_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         'C26 H25 F O6'
_chemical_formula_sum            'C26 H25 F O6'
_chemical_formula_weight         452.46
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-11-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 113.655(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.6310(4)
_cell_length_b                   9.89045(19)
_cell_length_c                   15.9579(4)
_cell_measurement_reflns_used    6825
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.5430
_cell_measurement_theta_min      5.1240
_cell_volume                     2259.77(11)
_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  '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_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.973
_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      3.00  28.00   0.50    0.50    --    0.00  19.00 -30.00   50
  2  \w    -20.00  21.00   0.50    0.50    --    0.00 -57.00  60.00   82
  3  \w     48.00  78.00   0.50    0.50    --    0.00  38.00 -30.00   60
  4  \w    -89.00 -32.00   0.50    0.50    --    0.00 -38.00-120.00  114
  5  \w     -8.00  17.00   0.50    0.50    --    0.00 -38.00  60.00   50
  6  \w    -78.00 -53.00   0.50    0.50    --    0.00 -38.00  60.00   50
  7  \w     41.00  85.00   0.50    0.50    --    0.00  19.00 -30.00   88
  8  \w    146.00 179.00   0.50    0.84    --   95.20  30.00  60.00   66
  9  \w    101.00 170.00   0.50    0.84    --   95.20  30.00 120.00  138
 10  \w     89.00 119.00   0.50    0.84    --   95.20  30.00  60.00   60
 11  \w     22.00 112.00   0.50    0.84    --   95.20 -30.00 150.00  180
 12  \w     13.00 100.00   0.50    0.84    --   95.20 -45.00 150.00  174
 13  \w      6.00 114.00   0.50    0.84    --   95.20 -45.00 -30.00  216
 14  \w     90.00 180.00   0.50    0.84    --   95.20  30.00  90.00  180
 15  \w     16.00  44.00   0.50    0.84    --   95.20 -15.00 120.00   56
;
_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      -0.0207549000
_diffrn_orient_matrix_UB_12      0.0796796000
_diffrn_orient_matrix_UB_13      0.0727497000
_diffrn_orient_matrix_UB_21      -0.0863599000
_diffrn_orient_matrix_UB_22      0.0638322000
_diffrn_orient_matrix_UB_23      -0.0758901000
_diffrn_orient_matrix_UB_31      -0.0607565000
_diffrn_orient_matrix_UB_32      -0.1175827000
_diffrn_orient_matrix_UB_33      0.0080133000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0315
_diffrn_reflns_av_unetI/netI     0.0330
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            12302
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.725
_diffrn_reflns_theta_min         3.344
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.828
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68033
_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    1.330
_exptl_crystal_description       block
_exptl_crystal_F_000             952
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.242
_refine_diff_density_min         -0.231
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     310
_refine_ls_number_reflns         4447
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0435
_refine_ls_R_factor_gt           0.0387
_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^)+(0.0460P)^2^+0.7194P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0995
_refine_ls_wR_factor_ref         0.1026
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3932
_reflns_number_total             4447
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b05608_si_003.cif
_cod_data_source_block           f_1102
_cod_depositor_comments
'Adding full bibliography for 4517422--4517424.cif.'
_cod_original_cell_volume        2259.76(10)
_cod_database_code               4517422
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.98
_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. Others
 Sof(H2B)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=1-FVAR(1)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H2A)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C12(H12), C14(H14)
3.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C16(H16A,H16B)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2A), C2(H2B), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C22(H22),
 C23(H23), C24(H24), C25(H25), C26(H26)
3.d X=CH2 refined with riding coordinates:
 C1(H1A,H1B), C1A(H1AA,H1AB)
3.e Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C20(H20A,H20B,H20C)
;
_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 1.642
_oxdiff_exptl_absorpt_empirical_full_min 0.482