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_4135331
_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         'C19 H20 Cl N O2'
_chemical_formula_sum            'C19 H20 Cl N O2'
_chemical_formula_weight         329.81
_chemical_name_systematic        1
_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     dual
_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                 112.529(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.7050(6)
_cell_length_b                   5.1203(2)
_cell_length_c                   15.0401(7)
_cell_measurement_reflns_used    3903
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      71.4020
_cell_measurement_theta_min      3.1860
_cell_volume                     832.61(7)
_computing_cell_refinement       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_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_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.957
_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     37.00  80.00   0.50    0.30    --  102.25 -77.00  30.00   86
  2  \w     38.00 105.00   0.50    0.30    --  102.25 -77.00 -60.00  134
  3  \w     50.00 103.00   0.50    0.30    --  102.25 -77.00-120.00  106
  4  \w     35.00  80.00   0.50    0.30    --  102.25 -77.00-150.00   90
  5  \w     25.00  51.00   0.50    0.30    --  102.25 -45.00 -30.00   52
  6  \w     25.00  50.00   0.50    0.30    --  102.25 -45.00   0.00   50
  7  \w     25.00  50.00   0.50    0.30    --  102.25 -45.00  90.00   50
  8  \w     75.00 163.00   0.50    0.30    --  102.25  30.00 120.00  176
  9  \w    121.00 177.00   0.50    0.30    --  102.25  61.00 -60.00  112
 10  \w    -26.00  34.00   0.50    0.08    --  -43.10  19.00   0.00  120
 11  \w    -68.00 -19.00   0.50    0.30    --  -90.25  61.00-180.00   98
 12  \w    -26.00  34.00   0.50    0.08    --  -43.10  19.00 -60.00  120
 13  \w    -25.00  37.00   0.50    0.08    --  -43.10  19.00  60.00  124
 14  \w    -57.00 -15.00   0.50    0.30    --  -90.25  61.00   0.00   84
 15  \w    -43.00 -16.00   0.50    0.30    --  -90.25  45.00   0.00   54
 16  \w    -51.00 -26.00   0.50    0.30    --  -90.25  45.00  60.00   50
 17  \w    -69.00 -30.00   0.50    0.30    --  -90.25  61.00 150.00   78
 18  \w    -78.00 -12.00   0.50    0.08    --  -43.10 125.00 120.00  132
 19  \w    -82.00 -41.00   0.50    0.30    --  -90.25 125.00 150.00   82
 20  \w    -90.00 -63.00   0.50    0.30    --  -90.25 125.00   0.00   54
 21  \w    -52.00 -27.00   0.50    0.30    --  -90.25 125.00   0.00   50
 22  \w   -172.00 -37.00   0.50    0.30    --  -90.25 -15.00-150.00  270
 23  \w   -163.00-103.00   0.50    0.30    --  -90.25-125.00  60.00  120
 24  \w   -100.00 -75.00   0.50    0.30    --  -90.25-125.00  60.00   50
 25  \w   -103.00 -78.00   0.50    0.08    --  -43.10-125.00   0.00   50
 26  \w     43.00  73.00   0.50    0.30    --  102.25-125.00 120.00   60
 27  \w     78.00 117.00   0.50    0.30    --  102.25-125.00 120.00   78
 28  \w     35.00  77.00   0.50    0.08    --   43.10-125.00 150.00   84
 29  \w     90.00 115.00   0.50    0.30    --  102.25-125.00-180.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0106156000
_diffrn_orient_matrix_UB_12      0.0400519000
_diffrn_orient_matrix_UB_13      -0.1043642000
_diffrn_orient_matrix_UB_21      0.1415521000
_diffrn_orient_matrix_UB_22      -0.0239944000
_diffrn_orient_matrix_UB_23      0.0334962000
_diffrn_orient_matrix_UB_31      -0.0128057000
_diffrn_orient_matrix_UB_32      -0.2972530000
_diffrn_orient_matrix_UB_33      -0.0167756000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0437
_diffrn_reflns_av_unetI/netI     0.0357
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       3
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            6462
_diffrn_reflns_point_group_measured_fraction_full 0.738
_diffrn_reflns_point_group_measured_fraction_max 0.705
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.505
_diffrn_reflns_theta_min         3.181
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.100
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58548
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.80a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            white
_exptl_crystal_density_diffrn    1.316
_exptl_crystal_description       plate
_exptl_crystal_F_000             348
_exptl_crystal_preparation       1
_exptl_crystal_recrystallization_method a
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.429
_refine_diff_density_min         -0.205
_refine_diff_density_rms         0.062
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.019(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     209
_refine_ls_number_reflns         2313
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0408
_refine_ls_R_factor_gt           0.0403
_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^)+(0.0821P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1053
_refine_ls_wR_factor_ref         0.1059
_reflns_Friedel_coverage         0.319
_reflns_Friedel_fraction_full    0.418
_reflns_Friedel_fraction_max     0.387
_reflns_number_gt                2242
_reflns_number_total             2313
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c10471_si_001.cif
_cod_data_source_block           exp_197
_cod_database_code               4135331
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.817
_shelx_estimated_absorpt_t_min   0.571
_diffrn_oxdiff_digest_frames
;
01a6da0c946d11832f4f096915d8bc8e3f00050d76a
;
_diffrn_oxdiff_digest_hkl
;
0170ff40ec3240d76dac558f088233e2554efb
;
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_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:
 C00D(H00D)
2.b Secondary CH2 refined with riding coordinates:
 C00A(H00A,H00B), C00G(H00F,H00G), C00I(H00I,H00J)
2.c Aromatic/amide H refined with riding coordinates:
 N004(H004), C008(H008), C009(H009), C00C(H00C), C00E(H00E), C00H(H00H),
 C00J(H00K), C00K(H00L), C00L(H00M), C00M(H00N)
2.d Idealised Me refined as rotating group:
 C00N(H00O,H00P,H00Q)
;
_shelx_res_checksum              45551
_shelx_hkl_checksum              12357
_olex2_exptl_crystal_mounting_method 1
_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 2.243
_oxdiff_exptl_absorpt_empirical_full_min 0.372