Direct Enantioselective C(sp<sup>3</sup>)-H Acylation for the Synthesis of α-Amino Ketones.
Shu, Xiaomin; Huan, Leitao; Huang, Qian; Huo, Haohua; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c10471

data_4135330
_publ_section_title
;
 Direct Enantioselective C(sp<sup>3</sup>)-H Acylation for the Synthesis
 of \a-Amino Ketones.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c10471
_journal_year                    2020
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C16 H22 Br N O2'
_chemical_formula_sum            'C16 H22 Br N O2'
_chemical_formula_weight         340.25
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2020-09-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 110.509(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.8183(5)
_cell_length_b                   4.94497(16)
_cell_length_c                   14.9662(6)
_cell_measurement_reflns_used    5202
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      68.4080
_cell_measurement_theta_min      3.9560
_cell_volume                     819.20(6)
_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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4741
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.993
_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   -115.00  -9.00   1.00    1.00    --  -40.88 -77.00-180.00  106
  2  \w   -111.00 -85.00   1.00    1.00    --  -40.88 -77.00  90.00   26
  3  \w   -117.00 -68.00   1.00    1.00    --  -40.88 -77.00   0.00   49
  4  \w    -38.00 -11.00   1.00    1.00    --  -40.88 -77.00  90.00   27
  5  \w    -60.00  -7.00   1.00    1.00    --  -40.88 -77.00-120.00   53
  6  \w    -65.00  24.00   1.00    1.00    --  -40.88  37.00 150.00   89
  7  \w   -110.00 -84.00   1.00    1.00    --  -40.88 -77.00-120.00   26
  8  \w    -52.00 -16.00   1.00    1.00    --  -40.88 -37.00-150.00   36
  9  \w    -44.00  -9.00   1.00    1.00    --  -40.88 -77.00   0.00   35
 10  \w    -64.00  -7.00   1.00    1.00    --  -40.88 -77.00 -30.00   57
 11  \w   -114.00 -11.00   1.00    1.00    --  -40.88 -57.00  60.00  103
 12  \w     60.00 108.00   1.00    1.00    --   40.88 178.00  90.00   48
 13  \w     57.00 127.00   1.00    1.00    --   40.88 178.00 -30.00   70
 14  \w     63.00 103.00   1.00    1.00    --   96.81  77.00 -30.00   40
 15  \w    122.00 165.00   1.00    1.00    --   96.81  61.00  90.00   43
 16  \w     65.00 111.00   1.00    1.00    --   96.81  70.00-123.09   46
 17  \w     21.00 107.00   1.00    1.00    --   96.81 -94.00 120.00   86
 18  \w     63.00 111.00   1.00    1.00    --   96.81  77.00-150.00   48
 19  \w    106.00 175.00   1.00    1.00    --   96.81  77.00 -65.54   69
 20  \w     64.00  96.00   1.00    1.00    --   96.81  75.00  41.35   32
 21  \w     64.00  89.00   1.00    1.00    --   96.81  77.00  90.00   25
 22  \w     63.00 171.00   1.00    1.00    --   96.81  77.00   0.00  108
 23  \w     63.00  89.00   1.00    1.00    --   96.81  77.00 -65.54   26
 24  \w     94.00 171.00   1.00    1.00    --   96.81 125.00-180.00   77
 25  \w     36.00 129.00   1.00    1.00    --   96.81 -77.00-180.00   93
 26  \w     69.00 115.00   1.00    1.00    --   96.81  61.00  90.00   46
 27  \w     64.00 176.00   1.00    1.00    --   96.81  77.00 150.00  112
 28  \w     63.00 133.00   1.00    1.00    --   96.81  77.00-180.00   70
 29  \w     70.00 170.00   1.00    1.00    --   96.81  61.00 -90.00  100
 30  \w    106.00 152.00   1.00    1.00    --   96.81  77.00 -30.00   46
 31  \w     66.00  96.00   1.00    1.00    --   96.81  61.00 -30.00   30
 32  \w     72.00  98.00   1.00    1.00    --   96.81  61.00 -60.00   26
 33  \w    117.00 142.00   1.00    1.00    --   96.81  70.00-123.09   25
 34  \w    101.00 171.00   1.00    1.00    --   96.81  75.00  41.35   70
 35  \w     64.00  95.00   1.00    1.00    --   96.81  77.00  60.00   31
 36  \w     67.00 112.00   1.00    1.00    --   96.81  61.00 150.00   45
 37  \w     31.00 116.00   1.00    1.00    --   96.81-125.00  30.00   85
 38  \w     64.00  96.00   1.00    1.00    --   96.81  71.00 120.07   32
 39  \w     65.00  91.00   1.00    1.00    --   96.81  70.00  25.00   26
;
_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      0.0033446000
_diffrn_orient_matrix_UB_12      0.1669442000
_diffrn_orient_matrix_UB_13      0.0878280000
_diffrn_orient_matrix_UB_21      0.0973759000
_diffrn_orient_matrix_UB_22      -0.1905168000
_diffrn_orient_matrix_UB_23      0.0649633000
_diffrn_orient_matrix_UB_31      0.0993187000
_diffrn_orient_matrix_UB_32      0.1813401000
_diffrn_orient_matrix_UB_33      -0.0125897000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0630
_diffrn_reflns_av_unetI/netI     0.0462
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            10691
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.349
_diffrn_reflns_theta_min         3.994
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.426
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.43076
_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_density_diffrn    1.379
_exptl_crystal_description       plate
_exptl_crystal_F_000             352
_refine_diff_density_max         0.463
_refine_diff_density_min         -0.451
_refine_diff_density_rms         0.075
_refine_ls_abs_structure_details
;
 Flack x determined using 1113 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     182
_refine_ls_number_reflns         2944
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0458
_refine_ls_R_factor_gt           0.0424
_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^)+(0.0622P)^2^+0.4394P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1063
_refine_ls_wR_factor_ref         0.1095
_reflns_Friedel_coverage         0.761
_reflns_Friedel_fraction_full    0.984
_reflns_Friedel_fraction_max     0.973
_reflns_number_gt                2760
_reflns_number_total             2944
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c10471_si_002.cif
_cod_data_source_block           exp_11179
_cod_original_cell_volume        819.21(6)
_cod_database_code               4135330
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     63.60
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C7(H7A,H7B), C9(H9A,H9B), C16(H16A,H16B), C20(H20A,
 H20B)
2.c Aromatic/amide H refined with riding coordinates:
 N6(H6), C11(H11), C14(H14), C18(H18), C22(H22), C0AA(H0AA)
2.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_shelx_res_checksum              76782
_shelx_hkl_checksum              80363
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.743
_oxdiff_exptl_absorpt_empirical_full_min 0.486