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_4038699
_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         'C21 H21 N O3 S'
_chemical_formula_sum            'C21 H21 N O3 S'
_chemical_formula_weight         367.45
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-07-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 109.4672(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.55924(6)
_cell_length_b                   5.55118(3)
_cell_length_c                   13.81508(7)
_cell_measurement_reflns_used    63384
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.4120
_cell_measurement_theta_min      3.3450
_cell_volume                     908.106(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.57a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.57a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.57a (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 1.000
_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    -66.00  33.00   1.00    1.00    --  -41.82  37.00 150.00   99
  2  \w   -114.00 -14.00   1.00    1.00    --  -41.82 -57.00 -90.00  100
  3  \w   -114.00 -68.00   1.00    1.00    --  -41.82-139.00  69.00   46
  4  \w   -114.00 -14.00   1.00    1.00    --  -41.82 -57.00-180.00  100
  5  \w      8.00  42.00   1.00    1.00    --   41.82  82.00 167.13   34
  6  \w     17.00 116.00   1.00    1.00    --   41.82  37.00-180.00   99
  7  \w      6.00  83.00   1.00    1.00    --   41.82 -99.00 120.00   77
  8  \w     81.00 178.00   1.00    4.00    --  107.00  45.00 -90.00   97
  9  \w     78.00 178.00   1.00    4.00    --  107.00  61.00 150.00  100
 10  \w     79.00 178.00   1.00    4.00    --  107.00  58.00 -70.58   99
 11  \w     34.00 112.00   1.00    4.00    --  107.00-125.00 150.00   78
 12  \w    103.00 178.00   1.00    4.00    --  107.00  77.00   0.00   75
 13  \w     81.00 178.00   1.00    4.00    --  107.00  45.00-180.00   97
 14  \w     78.00 178.00   1.00    4.00    --  107.00  61.00-150.00  100
 15  \w     78.00 178.00   1.00    4.00    --  107.00  61.00 -90.00  100
 16  \w     97.00 178.00   1.00    4.00    --  107.00 125.00 -90.00   81
 17  \w     78.00 178.00   1.00    4.00    --  107.00  61.00 -60.00  100
 18  \w     78.00 178.00   1.00    4.00    --  107.00  61.00-180.00  100
 19  \w     78.00 178.00   1.00    4.00    --  107.00  61.00-120.00  100
 20  \w     34.00 112.00   1.00    4.00    --  107.00-125.00  30.00   78
 21  \w     24.00 107.00   1.00    4.00    --  107.00 -94.00 -90.00   83
 22  \w     81.00 178.00   1.00    4.00    --  107.00  45.00-150.00   97
 23  \w     81.00 178.00   1.00    4.00    --  107.00  45.00-120.00   97
 24  \w     24.00 107.00   1.00    4.00    --  107.00 -94.00  30.00   83
 25  \w     81.00 178.00   1.00    4.00    --  107.00  45.00 -30.00   97
 26  \w     77.00 178.00   1.00    4.00    --  107.00  64.00  52.89  101
 27  \w     79.00 178.00   1.00    4.00    --  107.00  55.00 177.28   99
 28  \w     78.00 178.00   1.00    4.00    --  107.00  61.00 -30.00  100
 29  \w     78.00 178.00   1.00    4.00    --  107.00  61.00 120.00  100
 30  \w     77.00 178.00   1.00    4.00    --  107.00  65.00 105.17  101
 31  \w   -114.00 -14.00   1.00    1.00    --  -41.82 -57.00  30.00  100
 32  \w    -87.00  -6.00   1.00    1.00    --  -41.82 125.00-120.00   81
 33  \w      9.00  42.00   1.00    1.00    --   41.82  80.00 -62.39   33
 34  \w      6.00  83.00   1.00    1.00    --   41.82 -99.00  30.00   77
 35  \w      8.00  42.00   1.00    1.00    --   41.82  81.00 136.08   34
 36  \w      9.00  42.00   1.00    1.00    --   41.82  80.00   8.66   33
 37  \w      9.00  42.00   1.00    1.00    --   41.82  80.00  70.78   33
 38  \w     34.00 133.00   1.00    4.00    --  107.00 -45.00   0.00   99
 39  \w     81.00 178.00   1.00    4.00    --  107.00  45.00 120.00   97
 40  \w     31.00 140.00   1.00    4.00    --  107.00 -77.00 -60.00  109
 41  \w     31.00 140.00   1.00    4.00    --  107.00 -77.00-180.00  109
 42  \w     77.00 178.00   1.00    4.00    --  107.00  66.00  61.41  101
 43  \w     31.00 140.00   1.00    4.00    --  107.00 -77.00 -90.00  109
 44  \w     97.00 178.00   1.00    4.00    --  107.00 125.00 -60.00   81
 45  \w     78.00 178.00   1.00    4.00    --  107.00  61.00  30.00  100
 46  \w     81.00 178.00   1.00    4.00    --  107.00  45.00  60.00   97
 47  \w     78.00 178.00   1.00    4.00    --  107.00  61.00  90.00  100
 48  \w     81.00 178.00   1.00    4.00    --  107.00  45.00 150.00   97
 49  \w     81.00 178.00   1.00    4.00    --  107.00  45.00   0.00   97
 50  \w     81.00 178.00   1.00    4.00    --  107.00  45.00  90.00   97
 51  \w     34.00 112.00   1.00    4.00    --  107.00-125.00 -60.00   78
 52  \w     81.00 178.00   1.00    4.00    --  107.00  45.00  30.00   97
 53  \w     24.00 107.00   1.00    4.00    --  107.00 -94.00-150.00   83
 54  \w     35.00 136.00   1.00    4.00    --  107.00 -61.00-180.00  101
 55  \w     31.00 140.00   1.00    4.00    --  107.00 -77.00-150.00  109
 56  \w     31.00 140.00   1.00    4.00    --  107.00 -77.00-120.00  109
 57  \w     80.00 178.00   1.00    4.00    --  107.00  51.00  33.73   98
 58  \w     78.00 178.00   1.00    4.00    --  107.00  61.00   0.00  100
 59  \w   -114.00 -14.00   1.00    1.00    --  -41.82 -57.00 150.00  100
 60  \w   -114.00 -14.00   1.00    1.00    --  -41.82 -57.00  90.00  100
 61  \w   -114.00 -14.00   1.00    1.00    --  -41.82 -57.00 -60.00  100
 62  \w    -74.00  34.00   1.00    1.00    --  -41.82  77.00-180.00  108
 63  \w      6.00  83.00   1.00    1.00    --   41.82 -99.00-120.00   77
 64  \w      8.00  34.00   1.00    1.00    --   41.82  83.00-135.07   26
 65  \w      8.00  34.00   1.00    1.00    --   41.82  83.00  53.58   26
 66  \w     31.00  72.00   1.00    4.00    --  107.00 -77.00 -30.00   41
 67  \w     86.00 112.00   1.00    4.00    --  107.00 -77.00  90.00   26
 68  \w     34.00  60.00   1.00    4.00    --  107.00 -77.00  90.00   26
 69  \w     78.00 104.00   1.00    4.00    --  107.00  67.00-112.85   26
 70  \w     82.00 108.00   1.00    4.00    --  107.00  45.00 146.89   26
 71  \w     16.00  41.00   1.00    1.00    --   50.00  82.00 -87.88   25
 72  \w     16.00  41.00   1.00    1.00    --   50.00  81.00 -11.89   25
 73  \w     16.00  41.00   1.00    1.00    --   50.00  82.00-164.94   25
 74  \w     36.00  71.00   1.00    1.00    --   62.00  72.00 -93.05   35
 75  \w     30.00  56.00   1.00    1.00    --   62.00  73.00 128.90   26
 76  \w     31.00  57.00   1.00    1.00    --   62.00  72.00 172.98   26
 77  \w     31.00  57.00   1.00    1.00    --   62.00  71.00-133.92   26
 78  \w     31.00  57.00   1.00    1.00    --   62.00  72.00  42.65   26
 79  \w     33.00  62.00   1.00    1.00    --   62.00  72.00 -21.73   29
 80  \w     34.00  72.00   1.00    1.00    --   66.00  73.00  79.47   38
 81  \w     47.00  73.00   1.00    1.00    --   74.00  64.00-112.13   26
 82  \w     49.00  79.00   1.00    4.00    --   78.00  59.00  13.67   30
 83  \w     69.00  95.00   1.00    4.00    --   98.00  65.00 158.15   26
 84  \w    -80.00 -29.00   1.00    1.00    --    2.00 167.00-132.69   51
 85  \w     16.00  42.00   1.00    1.00    --   50.00  82.00-164.94   26
 86  \w     16.00  42.00   1.00    1.00    --   50.00  81.00 -11.89   26
 87  \w     16.00  42.00   1.00    1.00    --   50.00  81.00 162.92   26
 88  \w     16.00  42.00   1.00    1.00    --   50.00  82.00-115.72   26
 89  \w     16.00  42.00   1.00    1.00    --   50.00  81.00 -59.71   26
 90  \w     16.00  42.00   1.00    1.00    --   50.00  82.00 111.58   26
 91  \w     23.00 128.00   1.00    1.00    --   54.00  72.00  15.31  105
 92  \w     23.00 128.00   1.00    1.00    --   54.00  71.00 -56.67  105
 93  \w     22.00 129.00   1.00    1.00    --   54.00  73.00-170.18  107
 94  \w     28.00 131.00   1.00    1.00    --   58.00  66.00 -28.10  103
 95  \w     28.00 131.00   1.00    1.00    --   58.00  66.00-145.94  103
 96  \w     31.00 136.00   1.00    1.00    --   62.00  72.00 111.07  105
 97  \w     30.00 137.00   1.00    1.00    --   62.00  74.00  13.40  107
 98  \w     31.00 136.00   1.00    1.00    --   62.00  72.00 -93.05  105
 99  \w     31.00 136.00   1.00    1.00    --   62.00  71.00-133.92  105
100  \w     30.00 137.00   1.00    1.00    --   62.00  73.00 128.90  107
101  \w     31.00 136.00   1.00    1.00    --   62.00  72.00  42.65  105
102  \w     31.00 136.00   1.00    1.00    --   62.00  72.00  79.58  105
103  \w     31.00 136.00   1.00    1.00    --   62.00  72.00 -21.73  105
104  \w     34.00 141.00   1.00    1.00    --   66.00  73.00  79.47  107
105  \w     44.00 147.00   1.00    1.00    --   74.00  64.00-112.13  103
106  \w     49.00 151.00   1.00    4.00    --   78.00  59.00  13.67  102
107  \w     68.00 171.00   1.00    4.00    --   98.00  65.00 158.15  103
108  \w     34.00 112.00   1.00    4.00    --  107.00-125.00 -30.00   78
109  \w    103.00 178.00   1.00    4.00    --  107.00  77.00-150.00   75
110  \w     25.00 142.00   1.00    4.00    --  107.00 -86.00 -81.09  117
111  \w     97.00 178.00   1.00    4.00    --  107.00 125.00-150.00   81
112  \w    103.00 178.00   1.00    4.00    --  107.00  77.00-120.00   75
113  \w     34.00 112.00   1.00    4.00    --  107.00-125.00  90.00   78
114  \w     35.00 136.00   1.00    4.00    --  107.00 -61.00   0.00  101
115  \w     80.00 106.00   1.00    6.00    --  107.00  65.00 -52.09   26
116  \w     80.00 106.00   1.00    6.00    --  107.00  55.00-124.89   26
117  \w     51.00  76.00   1.00    6.00    --   82.00  69.00 -66.47   25
118  \w     63.00  88.00   1.00    6.00    --   90.00  52.00-133.39   25
119  \w     52.00  77.00   1.00    6.00    --   82.00  64.00  35.41   25
120  \w    -74.00  34.00   1.00    1.00    --  -41.82  77.00 -90.00  108
121  \w    -74.00  34.00   1.00    1.00    --  -41.82  77.00 -60.00  108
122  \w    -74.00  34.00   1.00    1.00    --  -41.82  77.00   0.00  108
123  \w    -74.00  34.00   1.00    1.00    --  -41.82  77.00 150.00  108
124  \w    -74.00  34.00   1.00    1.00    --  -41.82  77.00-120.00  108
125  \w    -74.00  34.00   1.00    1.00    --  -41.82  77.00 120.00  108
126  \w    -74.00  34.00   1.00    1.00    --  -41.82  77.00-180.00  108
127  \w    -74.00  34.00   1.00    1.00    --  -41.82  77.00  90.00  108
128  \w    -74.00  34.00   1.00    1.00    --  -41.82  77.00-180.00  108
129  \w    -74.00  34.00   1.00    1.00    --  -41.82  77.00  30.00  108
130  \w    -74.00  34.00   1.00    1.00    --  -41.82  77.00  60.00  108
131  \w    -74.00  34.00   1.00    1.00    --  -41.82  77.00-150.00  108
132  \w    -74.00  34.00   1.00    1.00    --  -41.82  77.00 -30.00  108
133  \w     23.00 128.00   1.00    1.00    --   54.00  71.00 -56.67  105
134  \w     23.00 128.00   1.00    1.00    --   54.00  72.00  15.31  105
135  \w     22.00 129.00   1.00    1.00    --   54.00  74.00 -39.29  107
136  \w     22.00 129.00   1.00    1.00    --   54.00  73.00-170.18  107
137  \w     26.00 133.00   1.00    1.00    --   58.00  74.00 124.63  107
138  \w     28.00 131.00   1.00    1.00    --   58.00  66.00 -28.10  103
139  \w     31.00 136.00   1.00    1.00    --   62.00  72.00  79.58  105
140  \w     31.00 136.00   1.00    1.00    --   62.00  72.00  42.65  105
141  \w     31.00 136.00   1.00    1.00    --   62.00  71.00-133.92  105
142  \w     31.00 136.00   1.00    1.00    --   62.00  72.00 -93.05  105
143  \w     31.00 136.00   1.00    1.00    --   62.00  72.00 111.07  105
144  \w     30.00 137.00   1.00    1.00    --   62.00  73.00 128.90  107
145  \w     30.00 137.00   1.00    1.00    --   62.00  74.00  13.40  107
146  \w     31.00 136.00   1.00    1.00    --   62.00  72.00 -21.73  105
147  \w     34.00 141.00   1.00    1.00    --   66.00  73.00  79.47  107
148  \w     42.00 142.00   1.00    1.00    --   70.00  55.00  12.82  100
149  \w     39.00 144.00   1.00    1.00    --   70.00  72.00  35.33  105
150  \w     38.00 145.00   1.00    1.00    --   70.00  74.00-108.94  107
151  \w     39.00 144.00   1.00    1.00    --   70.00  70.00 109.72  105
152  \w     49.00 151.00   1.00    6.00    --   78.00  60.00 -38.67  102
153  \w     52.00 155.00   1.00    6.00    --   82.00  64.00  35.41  103
154  \w     57.00 159.00   1.00    6.00    --   86.00  59.00 176.02  102
155  \w     64.00 163.00   1.00    6.00    --   90.00  47.00-107.43   99
156  \w     61.00 163.00   1.00    6.00    --   90.00  63.00-167.48  102
157  \w     64.00 167.00   1.00    6.00    --   94.00  65.00  14.84  103
158  \w     24.00 107.00   1.00    6.00    --  107.00 -94.00   0.00   83
159  \w     34.00 112.00   1.00    6.00    --  107.00-125.00 120.00   78
;
_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      -0.1129370000
_diffrn_orient_matrix_UB_12      0.0178327000
_diffrn_orient_matrix_UB_13      0.0206828000
_diffrn_orient_matrix_UB_21      -0.0637884000
_diffrn_orient_matrix_UB_22      0.0122691000
_diffrn_orient_matrix_UB_23      -0.1163785000
_diffrn_orient_matrix_UB_31      -0.0100939000
_diffrn_orient_matrix_UB_32      -0.2766960000
_diffrn_orient_matrix_UB_33      -0.0038375000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0503
_diffrn_reflns_av_unetI/netI     0.0124
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            75156
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.692
_diffrn_reflns_theta_min         3.393
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.752
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.37610
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.57a (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    1.344
_exptl_crystal_description       block
_exptl_crystal_F_000             388
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.181
_refine_diff_density_min         -0.373
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 1497 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
 Flack x: -0.001(10) Shelx 2018
 Hooft y: -0.016(3) Olex2

;
_refine_ls_abs_structure_Flack   -0.001(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     237
_refine_ls_number_reflns         3540
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0325
_refine_ls_R_factor_gt           0.0325
_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^)+(0.0620P)^2^+0.2293P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0905
_refine_ls_wR_factor_ref         0.0905
_reflns_Friedel_coverage         0.747
_reflns_Friedel_fraction_full    0.947
_reflns_Friedel_fraction_max     0.931
_reflns_number_gt                3535
_reflns_number_total             3540
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c01438_si_002.cif
_cod_data_source_block           skg1
_cod_original_cell_volume        908.107(8)
_cod_database_code               4038699
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H20 N2 O2 S'
_shelx_estimated_absorpt_t_max   0.902
_shelx_estimated_absorpt_t_min   0.621
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
The NH and OH were located in a difference map but refined with distance restraints AFIX 3 and AFIX 147 respectively
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.a Riding coordinates:
 N9(H9)
2.b Ternary CH refined with riding coordinates:
 C11(H11A), C10(H10)
2.c Aromatic/amide H refined with riding coordinates:
 C23(H23), C3(H3), C4(H4), C21(H21), C19(H19), C7(H7), C6(H6), C22(H22),
 C20(H20), C17(H17), C13(H13), C16(H16), C15(H15), C14(H14)
2.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
2.e Idealised tetrahedral OH refined as rotating group:
 O11(H11)
;
_shelx_res_checksum              79609
_shelx_hkl_checksum              5879
_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 1.855
_oxdiff_exptl_absorpt_empirical_full_min 0.525