Catalytic Asymmetric Synthesis of Quaternary Trifluoromethyl α- to ϵ-Amino Acid Derivatives via Umpolung Allylation/2-aza-Cope Rearrangement
Sun, Xi-Shang; Wang, Xing-Heng; Tao, Hai-Yan; Wei, Liang; Wang, Chun-Jiang; Chemical Science  (2020) –; doi:10.1039/D0SC04685J

data_1559110
_publ_section_title
;
 Catalytic Asymmetric Synthesis of Quaternary Trifluoromethyl \a- to
 &#x03F5;-Amino Acid Derivatives via Umpolung Allylation/2-aza-Cope
 Rearrangement
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC04685J
_journal_year                    2020
_chemical_formula_moiety         'C14 H13 F3 N2 O3'
_chemical_formula_sum            'C14 H13 F3 N2 O3'
_chemical_formula_weight         314.26
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-07-22 deposited with the CCDC.	2020-09-17 downloaded from the CCDC.
;
_cell_angle_alpha                64.933(2)
_cell_angle_beta                 83.768(2)
_cell_angle_gamma                83.692(2)
_cell_formula_units_Z            4
_cell_length_a                   7.36180(10)
_cell_length_b                   14.3967(4)
_cell_length_c                   14.8046(3)
_cell_measurement_reflns_used    26378
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.6980
_cell_measurement_theta_min      3.2900
_cell_volume                     1409.33(6)
_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 0.996
_diffrn_measured_fraction_theta_max 0.979
_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    -72.00 -29.00   0.50    0.50    --    0.00 -34.00 -60.00   86
  2  \w     -6.00  20.00   0.50    0.50    --    0.00  34.00  97.00   52
  3  \w     78.00 183.00   0.50    0.50    --   94.60  34.00  97.00  210
  4  \w     48.00  76.00   0.50    0.50    --   94.60 -34.00 -60.00   56
  5  \w    -44.00 -14.00   0.50    0.50    --    0.00 -77.00 -60.00   60
  6  \w    -17.00  37.00   0.50    0.50    --    0.00  38.00 120.00  108
  7  \w    -16.00  19.00   0.50    0.50    --    0.00  38.00 -90.00   70
  8  \w      2.00  28.00   0.50    0.50    --    0.00 -77.00 -60.00   52
  9  \w     37.00  73.00   0.50    0.50    --    0.00  19.00-120.00   72
 10  \w    -45.00 -16.00   0.50    0.50    --    0.00 -77.00 -30.00   58
 11  \w     35.00  65.00   0.50    0.50    --    0.00  38.00 -60.00   60
 12  \w     44.00  84.00   0.50    0.50    --    0.00  38.00 -90.00   80
 13  \w      3.00  28.00   0.50    0.50    --    0.00 -77.00 -30.00   50
 14  \w    -86.00 -53.00   0.50    0.50    --    0.00 -57.00  60.00   66
 15  \w     40.00  88.00   0.50    0.50    --    0.00  38.00 120.00   96
 16  \w    -17.00  11.00   0.50    0.50    --    0.00  38.00 -60.00   56
 17  \w    -17.00  25.00   0.50    0.50    --    0.00  19.00-120.00   84
 18  \w    -33.00  30.00   0.50    0.50    --    0.00 -82.00 120.00  126
 19  \w    -20.00  22.00   0.50    0.50    --    0.00 -57.00  60.00   84
 20  \w     68.00 109.00   0.50    0.50    --   94.60  71.00  45.13   82
 21  \w    106.00 184.00   0.50    0.50    --   94.60  73.00 112.69  156
 22  \w      5.00  47.00   0.50    0.50    --   94.60 -82.00 -60.00   84
 23  \w     67.00  93.00   0.50    0.50    --   94.60  73.00 112.69   52
 24  \w    156.00 183.00   0.50    0.50    --   94.60  61.00-180.00   54
 25  \w     71.00 123.00   0.50    0.50    --   94.60  61.00 -90.00  104
 26  \w    129.00 171.00   0.50    0.50    --   94.60  61.00 -60.00   84
 27  \w    143.00 184.00   0.50    0.50    --   94.60  71.00  93.14   82
 28  \w     70.00 101.00   0.50    0.50    --   94.60  64.00 -75.82   62
 29  \w     71.00 132.00   0.50    0.50    --   94.60  60.00 167.56  122
 30  \w     68.00  94.00   0.50    0.50    --   94.60  69.00  22.50   52
 31  \w     67.00  93.00   0.50    0.50    --   94.60  71.00 -33.94   52
 32  \w    154.00 184.00   0.50    0.50    --   94.60  71.00 -33.94   60
 33  \w     68.00  94.00   0.50    0.50    --   94.60  70.00  67.70   52
 34  \w     66.00  93.00   0.50    0.50    --   94.60  74.00 123.16   54
 35  \w     67.00 126.00   0.50    0.50    --   94.60  71.00  93.14  118
 36  \w    109.00 135.00   0.50    0.50    --   94.60  50.00 -92.90   52
 37  \w     71.00 150.00   0.50    0.50    --   94.60  61.00-180.00  158
 38  \w     74.00  99.00   0.50    0.50    --   94.60  50.00 -92.90   50
 39  \w      6.00 126.00   0.50    0.50    --   94.60 -82.00 120.00  240
 40  \w     69.00  95.00   0.50    0.50    --   94.60  68.00 -50.21   52
 41  \w    148.00 173.00   0.50    0.50    --   94.60  61.00 150.00   50
 42  \w     71.00 180.00   0.50    0.50    --   94.60  61.00 -30.00  218
 43  \w     67.00 105.00   0.50    0.50    --   94.60  71.00  32.68   76
 44  \w     67.00  92.00   0.50    0.50    --   94.60  71.00 -92.94   50
 45  \w     75.00 184.00   0.50    0.50    --   94.60  45.00  30.00  218
 46  \w     71.00  97.00   0.50    0.50    --   94.60  59.00  -1.03   52
 47  \w     53.00 125.00   0.50    0.50    --   94.60 -82.00 150.00  144
 48  \w     71.00  97.00   0.50    0.50    --   94.60  64.00-175.26   52
 49  \w     66.00 109.00   0.50    0.50    --   94.60  74.00-150.45   86
 50  \w     71.00  96.00   0.50    0.50    --   94.60  61.00  30.00   50
 51  \w     71.00 104.00   0.50    0.50    --   94.60  61.00 120.00   66
 52  \w     71.00  97.00   0.50    0.50    --   94.60  61.00  12.14   52
 53  \w    124.00 150.00   0.50    0.50    --   94.60  61.00  12.14   52
 54  \w     69.00 184.00   0.50    0.50    --   94.60  68.00-168.65  230
 55  \w     71.00 176.00   0.50    0.50    --   94.60  62.00 -51.26  210
 56  \w     29.00  97.00   0.50    0.50    --   94.60 -82.00  90.00  136
 57  \w     71.00  96.00   0.50    0.50    --   94.60  61.00-150.00   50
 58  \w    159.00 184.00   0.50    0.50    --   94.60  71.00  45.13   50
 59  \w    122.00 147.00   0.50    0.50    --   94.60  71.00  45.13   50
 60  \w     55.00 125.00   0.50    0.50    --   94.60 -82.00 -60.00  140
 61  \w     72.00 100.00   0.50    0.50    --   94.60  61.00 150.00   56
 62  \w     71.00 117.00   0.50    0.50    --   94.60  61.00 -60.00   92
 63  \w     71.00  96.00   0.50    0.50    --   94.60  61.00  90.00   50
 64  \w     67.00 172.00   0.50    0.50    --   94.60  71.00-131.57  210
 65  \w     53.00 116.00   0.50    0.50    --   94.60 -82.00   0.00  126
 66  \w     44.00 121.00   0.50    0.50    --   94.60 -82.00-150.00  154
;
_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      0.0045154000
_diffrn_orient_matrix_UB_12      0.0766790000
_diffrn_orient_matrix_UB_13      0.0471581000
_diffrn_orient_matrix_UB_21      0.2050122000
_diffrn_orient_matrix_UB_22      -0.0309632000
_diffrn_orient_matrix_UB_23      0.0160554000
_diffrn_orient_matrix_UB_31      0.0498746000
_diffrn_orient_matrix_UB_32      0.0847822000
_diffrn_orient_matrix_UB_33      -0.1038200000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0214
_diffrn_reflns_av_unetI/netI     0.0106
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            32442
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.961
_diffrn_reflns_theta_min         3.303
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.141
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64445
_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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.481
_exptl_crystal_description       plate
_exptl_crystal_F_000             648
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.269
_refine_diff_density_min         -0.328
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     401
_refine_ls_number_reflns         5607
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0327
_refine_ls_R_factor_gt           0.0322
_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^)+(0.0405P)^2^+0.5648P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0805
_refine_ls_wR_factor_ref         0.0809
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5444
_reflns_number_total             5607
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc04685j2.cif
_cod_data_source_block           20190304_sxs-7-94
_cod_depositor_comments
;

2022-05-15
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_moiety     '2(C14 H13 F3 N2 O3)'
_cod_original_formula_sum        'C28 H26 F6 N4 O6'
_cod_original_formula_units_Z    2
_cod_original_formula_weight     628.53
_cod_database_code               1559110
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.945
_shelx_estimated_absorpt_t_min   0.658
_reflns_odcompleteness_completeness 99.64
_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) groups
2.a Ternary CH refined with riding coordinates:
 C00T(H00T), C010(H010)
2.b Secondary CH2 refined with riding coordinates:
 C015(H01L,H01M), C017(H01A,H01B)
2.c Aromatic/amide H refined with riding coordinates:
 C00N(H00N), C00S(H00S), C00U(H00U), C00V(H00V), C00W(H00W), C00X(H00X),
 C011(H011), C012(H012)
2.d Idealised Me refined as rotating group:
 C00Z(H00A,H00B,H00C), C013(H01F,H01G,H01H), C014(H01I,H01J,H01K), C018(H01C,
 H01D,H01E)
;
_shelx_res_checksum              61505
_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 1.452
_oxdiff_exptl_absorpt_empirical_full_min 0.591