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_7126002
_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      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             2019-01-03
_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                 94.0216(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.25978(6)
_cell_length_b                   5.81649(4)
_cell_length_c                   12.31963(6)
_cell_measurement_reflns_used    13869
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.4860
_cell_measurement_theta_min      3.6190
_cell_volume                     804.855(8)
_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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.983
_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     57.00  89.00   0.50    0.50    --    0.00  57.00  30.00   64
  2  \w    -17.00   8.00   0.50    0.50    --    0.00  38.00  30.00   50
  3  \w      9.00  35.00   0.50    0.50    --    0.00  57.00  30.00   52
  4  \w     35.00  89.00   0.50    0.50    --    0.00  38.00 -60.00  108
  5  \w     -5.00  31.00   0.50    0.50    --    0.00 -82.00-150.00   72
  6  \w    -12.00  86.00   0.50    0.50    --    0.00  38.00 150.00  196
  7  \w     12.00  74.00   0.50    0.50    --    0.00  38.00  30.00  124
  8  \w     -4.00  31.00   0.50    0.50    --    0.00 -82.00 -60.00   70
  9  \w    -14.00  28.00   0.50    0.50    --    0.00  38.00 -60.00   84
 10  \w    -22.00   4.00   0.50    0.50    --    0.00  57.00  30.00   52
 11  \w    -29.00  -2.00   0.50    0.50    --    0.00 -82.00-180.00   54
 12  \w     69.00  95.00   0.50    0.50    --   94.60  67.00-136.38   52
 13  \w     69.00 103.00   0.50    0.50    --   94.60  68.00 139.51   68
 14  \w     70.00 128.00   0.50    0.50    --   94.60  65.00-170.10  116
 15  \w    139.00 180.00   0.50    0.50    --   94.60  72.00 -78.95   82
 16  \w     68.00  94.00   0.50    0.50    --   94.60  72.00 -78.95   52
 17  \w    112.00 184.00   0.50    0.50    --   94.60  67.00 -22.42  144
 18  \w     67.00  93.00   0.50    0.50    --   94.60  71.00 120.54   52
 19  \w     68.00  94.00   0.50    0.50    --   94.60  69.00 162.04   52
 20  \w     68.00 113.00   0.50    0.50    --   94.60  70.00-105.73   90
 21  \w     69.00 161.00   0.50    0.50    --   94.60  66.00  65.88  184
 22  \w    114.00 182.00   0.50    0.50    --   94.60  69.00 162.04  136
 23  \w      6.00 108.00   0.50    0.50    --   94.60 -61.00  90.00  204
 24  \w    150.00 175.00   0.50    0.50    --   94.60  61.00 104.87   50
 25  \w     75.00 124.00   0.50    0.50    --   94.60  45.00  60.00   98
 26  \w    126.00 151.00   0.50    0.50    --   94.60  45.00  60.00   50
 27  \w    150.00 175.00   0.50    0.50    --   94.60  64.00-109.80   50
 28  \w     69.00  95.00   0.50    0.50    --   94.60  67.00 -22.42   52
 29  \w      7.00 126.00   0.50    0.50    --   94.60 -82.00  90.00  238
 30  \w     63.00 126.00   0.50    0.50    --   94.60 -82.00-150.00  126
 31  \w     71.00 148.00   0.50    0.50    --   94.60  61.00 104.87  154
 32  \w    144.00 170.00   0.50    0.50    --   94.60  74.00 -63.65   52
 33  \w     70.00  96.00   0.50    0.50    --   94.60  64.00-109.80   52
 34  \w     19.00 125.00   0.50    0.50    --   94.60 -82.00 -60.00  212
 35  \w     66.00 109.00   0.50    0.50    --   94.60  74.00 -63.65   86
 36  \w    108.00 184.00   0.50    0.50    --   94.60  61.00   0.00  152
 37  \w     71.00  99.00   0.50    0.50    --   94.60  61.00 -30.00   56
 38  \w     75.00 131.00   0.50    0.50    --   94.60  61.00-150.00  112
 39  \w     71.00  97.00   0.50    0.50    --   94.60  61.00  90.00   52
 40  \w     76.00 164.00   0.50    0.50    --   94.60  45.00 -60.00  176
 41  \w     71.00  97.00   0.50    0.50    --   94.60  61.00-180.00   52
 42  \w     71.00 128.00   0.50    0.50    --   94.60  61.00-120.00  114
 43  \w     71.00 170.00   0.50    0.50    --   94.60  61.00 120.00  198
 44  \w     71.00  97.00   0.50    0.50    --   94.60  61.00  60.00   52
 45  \w     75.00 102.00   0.50    0.50    --   94.60 -82.00   0.00   54
 46  \w     56.00 104.00   0.50    0.50    --   94.60 -61.00-180.00   96
 47  \w     78.00 114.00   0.50    0.50    --   94.60  30.00   0.00   72
 48  \w     78.00 104.00   0.50    0.50    --   94.60  45.00-180.00   52
 49  \w     72.00 101.00   0.50    0.50    --   94.60  61.00   0.00   58
 50  \w    139.00 181.00   0.50    0.50    --   94.60  65.00-170.10   84
 51  \w    155.00 181.00   0.50    0.50    --   94.60  68.00 139.51   52
 52  \w     69.00 103.00   0.50    0.50    --   94.60  66.00  14.93   68
 53  \w    153.00 178.00   0.50    0.50    --   94.60  66.00  43.38   50
 54  \w     70.00  96.00   0.50    0.50    --   94.60  66.00  43.38   52
;
_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      -0.1333975000
_diffrn_orient_matrix_UB_12      0.0017972000
_diffrn_orient_matrix_UB_13      0.0204811000
_diffrn_orient_matrix_UB_21      0.0315941000
_diffrn_orient_matrix_UB_22      0.0400763000
_diffrn_orient_matrix_UB_23      0.1222040000
_diffrn_orient_matrix_UB_31      -0.0039194000
_diffrn_orient_matrix_UB_32      0.2618896000
_diffrn_orient_matrix_UB_33      -0.0188214000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0157
_diffrn_reflns_av_unetI/netI     0.0087
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            15374
_diffrn_reflns_point_group_measured_fraction_full 0.952
_diffrn_reflns_point_group_measured_fraction_max 0.935
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.664
_diffrn_reflns_theta_min         3.597
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.970
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79723
_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    1.392
_exptl_crystal_description       block
_exptl_crystal_F_000             352
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.243
_refine_diff_density_min         -0.258
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details
;
 Flack x determined using 1271 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     224
_refine_ls_number_reflns         3036
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0248
_refine_ls_R_factor_gt           0.0248
_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^)+(0.0387P)^2^+0.1757P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0665
_refine_ls_wR_factor_ref         0.0665
_reflns_Friedel_coverage         0.726
_reflns_Friedel_fraction_full    0.897
_reflns_Friedel_fraction_max     0.876
_reflns_number_gt                3033
_reflns_number_total             3036
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc00845a3.cif
_cod_data_source_block           20190103_sxs7641
_cod_depositor_comments
'Adding full bibliography for 7126002--7126003.cif.'
_cod_original_cell_volume        804.856(8)
_cod_database_code               7126002
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H00F,H00J} of C00J, {H00K,H00M} of C00M
 At 1.5 times of:
  All C(H,H,H) groups, {H00A,H00B} of C00O
2.a Ternary CH refined with riding coordinates:
 C00G(H00G)
2.b Secondary CH2 refined with riding coordinates:
 C00J(H00F,H00J)
2.c Aromatic/amide H refined with riding coordinates:
 C007(H007), C008(H008), C00B(H00C), C00C(H00D), C00E(H00E), C00H(H00H),
 C00I(H00I), C00L(H00L)
2.d X=CH2 refined with riding coordinates:
 C00M(H00K,H00M)
2.e Idealised Me refined as rotating group:
 C00N(H00N,H00O,H00P)
;
_shelx_res_checksum              51839
_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 1.263
_oxdiff_exptl_absorpt_empirical_full_min 0.774