Asymmetric synthesis of quaternary α-trifluoromethyl α-amino acids by Ir-catalyzed allylation followed by kinetic resolution.
Sun, Xi-Shang; Ou-Yang, Qiu; Xu, Shi-Ming; Wang, Xing-Heng; Tao, Hai-Yan; Chung, Lung Wa; Wang, Chun-Jiang; Chemical communications (Cambridge, England) 56 (2020) 3333–3336; doi:10.1039/d0cc00845a

data_7126003
_publ_section_title
;
 Asymmetric synthesis of quaternary \a-trifluoromethyl \a-amino acids by
 Ir-catalyzed allylation followed by kinetic resolution.
;
_journal_issue                   22
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              3333
_journal_page_last               3336
_journal_paper_doi               10.1039/d0cc00845a
_journal_volume                  56
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H18 F3 N O2'
_chemical_formula_sum            'C18 H18 F3 N O2'
_chemical_formula_weight         337.33
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-03
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-09-24 deposited with the CCDC.	2020-02-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.79020(10)
_cell_length_b                   8.67390(10)
_cell_length_c                   32.4787(4)
_cell_measurement_reflns_used    16134
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.5810
_cell_measurement_theta_min      5.1860
_cell_volume                     1631.20(4)
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_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     58.00  88.00   0.50    0.50    --    0.00  57.00 -60.00   60
  2  \w    -89.00 -27.00   0.50    0.50    --    0.00 -57.00   0.00  124
  3  \w     -1.00  53.00   0.50    0.50    --    0.00  57.00 -60.00  108
  4  \w     31.00  86.00   0.50    0.50    --    0.00  38.00 120.00  110
  5  \w     58.00  85.00   0.50    0.50    --    0.00  19.00 -60.00   54
  6  \w    -16.00  25.00   0.50    0.50    --    0.00  38.00 120.00   82
  7  \w    -18.00  47.00   0.50    0.50    --    0.00  19.00 -60.00  130
  8  \w    -21.00  24.00   0.50    0.50    --    0.00 -82.00-180.00   90
  9  \w     -6.00  31.00   0.50    0.50    --    0.00 -82.00  60.00   74
 10  \w    -17.00  84.00   0.50    0.50    --    0.00  38.00-150.00  202
 11  \w     -7.00  20.00   0.50    0.50    --    0.00 -57.00   0.00   54
 12  \w     71.00 107.00   0.50    0.50    --   94.60  59.00 105.86   72
 13  \w     71.00 184.00   0.50    0.50    --   94.60  59.00 -98.70  226
 14  \w    153.00 184.00   0.50    0.50    --   94.60  59.00 105.86   62
 15  \w     66.00  93.00   0.50    0.50    --   94.60  75.00  17.87   54
 16  \w     72.00  97.00   0.50    0.50    --   94.60  61.00-138.73   50
 17  \w    155.00 182.00   0.50    0.50    --   94.60  64.00 -77.94   54
 18  \w     71.00  96.00   0.50    0.50    --   94.60  65.00-130.07   50
 19  \w     69.00  99.00   0.50    0.50    --   94.60  68.00-120.39   60
 20  \w     70.00  96.00   0.50    0.50    --   94.60  64.00 -40.24   52
 21  \w     71.00 183.00   0.50    0.50    --   94.60  66.00 -60.75  224
 22  \w    139.00 182.00   0.50    0.50    --   94.60  68.00-120.39   86
 23  \w     68.00 182.00   0.50    0.50    --   94.60  69.00  46.10  228
 24  \w     70.00  96.00   0.50    0.50    --   94.60  64.00  -5.50   52
 25  \w      6.00 125.00   0.50    0.50    --   94.60 -82.00-150.00  238
 26  \w     69.00  94.00   0.50    0.50    --   94.60  70.00-102.28   50
 27  \w     12.00 123.00   0.50    0.50    --   94.60 -77.00 -30.00  222
 28  \w     72.00  99.00   0.50    0.50    --   94.60  61.00 170.34   54
 29  \w    103.00 184.00   0.50    0.50    --   94.60  61.00 170.34  162
 30  \w     65.00 115.00   0.50    0.50    --   94.60 -82.00 120.00  100
 31  \w     72.00 110.00   0.50    0.50    --   94.60  55.00 -33.53   76
 32  \w     70.00 139.00   0.50    0.50    --   94.60  64.00 -77.94  138
 33  \w     66.00  92.00   0.50    0.50    --   94.60  74.00 141.04   52
 34  \w     71.00  98.00   0.50    0.50    --   94.60  61.00  90.00   54
 35  \w     66.00  92.00   0.50    0.50    --   94.60  75.00  63.84   52
 36  \w     71.00 176.00   0.50    0.50    --   94.60  59.00  73.79  210
 37  \w     71.00  97.00   0.50    0.50    --   94.60  61.00 120.00   52
 38  \w      6.00 112.00   0.50    0.50    --   94.60 -61.00-150.00  212
 39  \w     71.00  98.00   0.50    0.50    --   94.60  61.00-180.00   54
 40  \w    133.00 159.00   0.50    0.50    --   94.60  61.00-180.00   52
 41  \w     71.00 144.00   0.50    0.50    --   94.60  61.00  30.00  146
 42  \w     41.00 126.00   0.50    0.50    --   94.60 -82.00   0.00  170
 43  \w     72.00  97.00   0.50    0.50    --   94.60  61.00 -30.00   50
 44  \w      6.00 110.00   0.50    0.50    --   94.60 -82.00  60.00  208
 45  \w     75.00 134.00   0.50    0.50    --   94.60  45.00 133.34  118
 46  \w     71.00 141.00   0.50    0.50    --   94.60  61.00 143.87  140
 47  \w     71.00  97.00   0.50    0.50    --   94.60  61.00-150.00   52
 48  \w     69.00 127.00   0.50    0.50    --   94.60  67.00   0.24  116
 49  \w     76.00 176.00   0.50    0.50    --   94.60  46.00-149.91  200
 50  \w    141.00 170.00   0.50    0.50    --   94.60  65.00-130.07   58
 51  \w    127.00 154.00   0.50    0.50    --   94.60  56.00  -8.16   54
 52  \w     72.00  99.00   0.50    0.50    --   94.60  56.00  -8.16   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.2512051000
_diffrn_orient_matrix_UB_12      0.0584465000
_diffrn_orient_matrix_UB_13      -0.0007641000
_diffrn_orient_matrix_UB_21      -0.0381617000
_diffrn_orient_matrix_UB_22      0.0802801000
_diffrn_orient_matrix_UB_23      0.0417397000
_diffrn_orient_matrix_UB_31      0.0790672000
_diffrn_orient_matrix_UB_32      -0.1471947000
_diffrn_orient_matrix_UB_33      0.0225306000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0434
_diffrn_reflns_av_unetI/netI     0.0173
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            32777
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.105
_diffrn_reflns_theta_min         2.721
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.958
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49838
_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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.374
_exptl_crystal_description       block
_exptl_crystal_F_000             704
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.127
_refine_diff_density_min         -0.129
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 1242 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.03(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     224
_refine_ls_number_reflns         3264
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0295
_refine_ls_R_factor_gt           0.0284
_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^)+(0.0335P)^2^+0.4333P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0697
_refine_ls_wR_factor_ref         0.0703
_reflns_Friedel_coverage         0.681
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.979
_reflns_number_gt                3158
_reflns_number_total             3264
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc00845a3.cif
_cod_data_source_block           20190103_sxs7642
_cod_depositor_comments
'Adding full bibliography for 7126002--7126003.cif.'
_cod_database_code               7126003
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.954
_shelx_estimated_absorpt_t_min   0.762
_reflns_odcompleteness_completeness 99.94
_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,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C00F(H00F)
2.b Secondary CH2 refined with riding coordinates:
 C00N(H00M,H00N)
2.c Aromatic/amide H refined with riding coordinates:
 C009(H009), C00A(H00C), C00B(H00D), C00G(H00G), C00I(H00I), C00J(H00J),
 C00K(H00K), C00L(H00L)
2.d X=CH2 refined with riding coordinates:
 C00M(H00E,H00H)
2.e Idealised Me refined as rotating group:
 C00O(H00O,H00P,H00Q)
;
_shelx_res_checksum              3731
_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 1.671
_oxdiff_exptl_absorpt_empirical_full_min 0.725