Asymmetric Transfer Hydrogenation: Dynamic Kinetic Resolution of α-Amino Ketones.
Gediya, Shweta K.; Clarkson, Guy J.; Wills, Martin; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c01438

data_4038698
_publ_section_title
;
 Asymmetric Transfer Hydrogenation: Dynamic Kinetic Resolution of \a-Amino
 Ketones.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c01438
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H22 Cl N O3'
_chemical_formula_sum            'C19 H22 Cl N O3'
_chemical_formula_weight         347.82
_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             2019-10-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.73271(10)
_cell_length_b                   10.62789(15)
_cell_length_c                   18.00805(18)
_cell_measurement_reflns_used    23370
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.5090
_cell_measurement_theta_min      4.8110
_cell_volume                     1862.72(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.61a (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      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3046
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_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   -116.00 -17.00   1.00    5.00    --  -41.82 -37.00 -60.00   99
  2  \w   -114.00 -14.00   1.00    5.00    --  -41.82 -57.00   0.00  100
  3  \w   -116.00 -17.00   1.00    5.00    --  -41.82 -37.00  30.00   99
  4  \w   -114.00 -14.00   1.00    5.00    --  -41.82 -57.00 -30.00  100
  5  \w   -116.00 -17.00   1.00    5.00    --  -41.82 -37.00   0.00   99
  6  \w     27.00  98.00   1.00    5.00    --   41.82-125.00-150.00   71
  7  \w      6.00  83.00   1.00    5.00    --   41.82 -99.00 -60.00   77
  8  \w     17.00 116.00   1.00    5.00    --   41.82  37.00  30.00   99
  9  \w      8.00  34.00   1.00    5.00    --   41.82  83.00  58.05   26
 10  \w    -33.00  66.00   1.00    5.00    --   41.82 -37.00-180.00   99
 11  \w      8.00  42.00   1.00    5.00    --   41.82  82.00 142.67   34
 12  \w     34.00 112.00   1.00   20.00    --  107.00-125.00  90.00   78
 13  \w     78.00 178.00   1.00   20.00    --  107.00  61.00  30.00  100
 14  \w     77.00 178.00   1.00   20.00    --  107.00  64.00  -3.52  101
 15  \w     81.00 178.00   1.00   20.00    --  107.00  45.00  60.00   97
 16  \w    103.00 178.00   1.00   20.00    --  107.00  77.00-150.00   75
 17  \w     78.00 178.00   1.00   20.00    --  107.00  60.00 104.17  100
 18  \w     79.00 178.00   1.00   20.00    --  107.00  56.00 140.38   99
 19  \w     78.00 178.00   1.00   20.00    --  107.00  61.00 120.00  100
 20  \w     78.00 178.00   1.00   20.00    --  107.00  61.00  60.00  100
 21  \w    103.00 178.00   1.00   20.00    --  107.00  77.00 -90.00   75
 22  \w     24.00 107.00   1.00   20.00    --  107.00 -94.00   0.00   83
 23  \w     81.00 178.00   1.00   20.00    --  107.00  45.00  90.00   97
 24  \w     78.00 178.00   1.00   20.00    --  107.00  62.00 -26.49  100
 25  \w     97.00 178.00   1.00   20.00    --  107.00 125.00 -60.00   81
 26  \w     97.00 178.00   1.00   20.00    --  107.00 125.00-120.00   81
 27  \w    103.00 178.00   1.00   20.00    --  107.00  77.00-120.00   75
 28  \w     78.00 178.00   1.00   20.00    --  107.00  61.00 150.00  100
 29  \w     81.00 178.00   1.00   20.00    --  107.00  45.00 150.00   97
 30  \w     31.00 140.00   1.00   20.00    --  107.00 -77.00 -30.00  109
 31  \w     27.00 107.00   1.00   20.00    --  107.00-100.00  68.77   80
 32  \w    103.00 178.00   1.00   20.00    --  107.00  77.00  60.00   75
 33  \w     24.00 107.00   1.00   20.00    --  107.00 -94.00 -90.00   83
 34  \w    103.00 178.00   1.00   20.00    --  107.00  77.00  30.00   75
 35  \w     81.00 178.00   1.00   20.00    --  107.00  45.00   0.00   97
 36  \w     81.00 178.00   1.00   20.00    --  107.00  45.00  30.00   97
 37  \w     34.00  84.00   1.00   20.00    --  107.00-125.00-120.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1538621000
_diffrn_orient_matrix_UB_12      -0.0166945000
_diffrn_orient_matrix_UB_13      0.0175538000
_diffrn_orient_matrix_UB_21      -0.0359708000
_diffrn_orient_matrix_UB_22      -0.0335626000
_diffrn_orient_matrix_UB_23      0.0809009000
_diffrn_orient_matrix_UB_31      -0.0097153000
_diffrn_orient_matrix_UB_32      -0.1400190000
_diffrn_orient_matrix_UB_33      -0.0215378000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0552
_diffrn_reflns_av_unetI/netI     0.0210
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            37550
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.768
_diffrn_reflns_theta_min         4.832
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.943
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.40353
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.61a (Rigaku Oxford Diffraction, 2019)
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    1.240
_exptl_crystal_description       block
_exptl_crystal_F_000             736
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.180
_refine_diff_density_min         -0.304
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 1512 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.001(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     261
_refine_ls_number_reflns         3762
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0402
_refine_ls_R_factor_gt           0.0378
_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^)+(0.0573P)^2^+0.3325P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0993
_refine_ls_wR_factor_ref         0.1014
_reflns_Friedel_coverage         0.742
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                3667
_reflns_number_total             3762
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c01438_si_003.cif
_cod_data_source_block           skg2
_cod_database_code               4038698
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H20 O2 Cl'
_shelx_estimated_absorpt_t_max   0.746
_shelx_estimated_absorpt_t_min   0.593
_reflns_odcompleteness_completeness 99.27
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.08
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 C17A-C18A = C17A-C19A = C17A-C20A
 1.5 with sigma of 0.02
 C17-C18 = C17-C19 = C17-C20
 1.5 with sigma of 0.02
3. Rigid body (RIGU) restrains
 H20E, H20F, H18D, C17A, C18A, H18E, H18F, C19A, H19D, H19E, H19F, C20A, H20D
 with sigma for 1-2 distances of 0.0008 and sigma for 1-3 distances of 0.0008
4. Others
 Sof(C17A)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C19A)=Sof(H19D)=
 Sof(H19E)=Sof(H19F)=Sof(C20A)=Sof(H20E)=Sof(H20F)=Sof(H20D)=1-FVAR(1)
 Sof(C17)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19C)=Sof(H19A)=
 Sof(H19B)=Sof(C20)=Sof(H20A)=Sof(H20C)=Sof(H20B)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C7(H7A), C8(H8A)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), N8(H8), C10(H10), C11(H11), C12(H12),
 C13(H13), C14(H14)
5.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C18A(H18D,H18E,H18F), C19(H19C,H19A,H19B), C19A(H19D,
 H19E,H19F), C20(H20A,H20C,H20B), C20A(H20E,H20F,H20D)
5.d Idealised tetrahedral OH refined as rotating group:
 O7(H7)
;
_shelx_res_checksum              68519
_shelx_hkl_checksum              6948
_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 2.177
_oxdiff_exptl_absorpt_empirical_full_min 0.388