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_1559111
_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_absolute_configuration unk
_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   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-04-14
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_audit_update_record
;
2020-07-22 deposited with the CCDC.	2020-09-17 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   6.2073(2)
_cell_length_b                   7.63800(10)
_cell_length_c                   34.6279(9)
_cell_measurement_reflns_used    12223
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      72.3370
_cell_measurement_theta_min      2.5640
_cell_volume                     1641.76(7)
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.973
_diffrn_measured_fraction_theta_max 0.974
_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    -17.00   9.00   0.50    0.50    --    0.00  38.00 -60.00   52
  2  \w    -21.00   5.00   0.50    0.50    --    0.00 -82.00-180.00   52
  3  \w     32.00  75.00   0.50    0.50    --    0.00  38.00  30.00   86
  4  \w    -18.00  58.00   0.50    0.50    --    0.00  19.00-180.00  152
  5  \w    -17.00  17.00   0.50    0.50    --    0.00  38.00  30.00   68
  6  \w     48.00  89.00   0.50    0.50    --    0.00  57.00-150.00   82
  7  \w    -22.00  32.00   0.50    0.50    --    0.00  57.00-150.00  108
  8  \w    -16.00  84.00   0.50    0.50    --    0.00  38.00  90.00  200
  9  \w    -16.00  31.00   0.50    0.50    --    0.00  38.00 -30.00   94
 10  \w     60.00  89.00   0.50    0.50    --    0.00  38.00 -30.00   58
 11  \w     68.00  93.00   0.50    0.50    --   94.60  71.00 -98.95   50
 12  \w     68.00  95.00   0.50    0.50    --   94.60  69.00 173.65   54
 13  \w    150.00 179.00   0.50    0.50    --   94.60  69.00 173.65   58
 14  \w     68.00  94.00   0.50    0.50    --   94.60  70.00 -83.13   52
 15  \w     70.00 136.00   0.50    0.50    --   94.60  66.00  94.93  132
 16  \w    135.00 183.00   0.50    0.50    --   94.60  40.00  23.48   96
 17  \w     69.00  95.00   0.50    0.50    --   94.60  66.00-149.97   52
 18  \w     67.00 180.00   0.50    0.50    --   94.60  75.00 -63.50  226
 19  \w     67.00 147.00   0.50    0.50    --   94.60  72.00-169.82  160
 20  \w    107.00 184.00   0.50    0.50    --   94.60  59.00 130.27  154
 21  \w     69.00  95.00   0.50    0.50    --   94.60  66.00 158.35   52
 22  \w     66.00  98.00   0.50    0.50    --   94.60  74.00  65.98   64
 23  \w     71.00 103.00   0.50    0.50    --   94.60  61.00  46.77   64
 24  \w    134.00 183.00   0.50    0.50    --   94.60  61.00  46.77   98
 25  \w     68.00  94.00   0.50    0.50    --   94.60  69.00-130.47   52
 26  \w    120.00 146.00   0.50    0.50    --   94.60  69.00-130.47   52
 27  \w    156.00 182.00   0.50    0.50    --   94.60  69.00-130.47   52
 28  \w     66.00  92.00   0.50    0.50    --   94.60  74.00-115.68   52
 29  \w     77.00 104.00   0.50    0.50    --   94.60  40.00  23.48   54
 30  \w     17.00 126.00   0.50    0.50    --   94.60 -82.00  30.00  218
 31  \w     71.00  98.00   0.50    0.50    --   94.60  59.00 130.27   54
 32  \w     67.00 129.00   0.50    0.50    --   94.60  71.00 -71.42  124
 33  \w    113.00 179.00   0.50    0.50    --   94.60  69.00 -43.75  132
 34  \w     72.00  97.00   0.50    0.50    --   94.60  61.00  60.00   50
 35  \w     70.00  96.00   0.50    0.50    --   94.60  63.00 139.92   52
 36  \w     71.00  97.00   0.50    0.50    --   94.60  61.00  30.00   52
 37  \w     71.00  96.00   0.50    0.50    --   94.60  61.00   0.00   50
 38  \w    124.00 184.00   0.50    0.50    --   94.60  61.00   0.00  120
 39  \w     55.00 112.00   0.50    0.50    --   94.60 -61.00 120.00  114
 40  \w     70.00 131.00   0.50    0.50    --   94.60  63.00 177.22  122
 41  \w     74.00 102.00   0.50    0.50    --   94.60  61.00 150.00   56
 42  \w    106.00 184.00   0.50    0.50    --   94.60  70.00 105.13  156
 43  \w     77.00 102.00   0.50    0.50    --   94.60  45.00   0.00   50
 44  \w     72.00  97.00   0.50    0.50    --   94.60  61.00  90.00   50
 45  \w     29.00  63.00   0.50    0.50    --   94.60 -82.00 -60.00   68
 46  \w     75.00 126.00   0.50    0.50    --   94.60 -82.00 -60.00  102
 47  \w     51.00 126.00   0.50    0.50    --   94.60 -82.00 120.00  150
 48  \w     68.00  93.00   0.50    0.50    --   94.60  70.00 105.13   50
 49  \w     69.00  95.00   0.50    0.50    --   94.60  69.00 -43.75   52
 50  \w     71.00 177.00   0.50    0.50    --   94.60  63.00-138.06  212
 51  \w     75.00 116.00   0.50    0.50    --   94.60  47.00  33.33   82
 52  \w     22.00 114.00   0.50    0.50    --   94.60 -82.00 -90.00  184
 53  \w     68.00 181.00   0.50    0.50    --   94.60  69.00-116.74  226
;
_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      0.0126550000
_diffrn_orient_matrix_UB_12      -0.0871154000
_diffrn_orient_matrix_UB_13      -0.0400346000
_diffrn_orient_matrix_UB_21      -0.0277903000
_diffrn_orient_matrix_UB_22      -0.1812733000
_diffrn_orient_matrix_UB_23      0.0189126000
_diffrn_orient_matrix_UB_31      -0.2463053000
_diffrn_orient_matrix_UB_32      0.0159414000
_diffrn_orient_matrix_UB_33      -0.0042081000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0698
_diffrn_reflns_av_unetI/netI     0.0229
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            28850
_diffrn_reflns_theta_full        66.50
_diffrn_reflns_theta_max         67.48
_diffrn_reflns_theta_min         2.55
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.951
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57098
_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            Colourless
_exptl_crystal_density_diffrn    1.365
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             704
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.405
_refine_diff_density_min         -0.459
_refine_diff_density_rms         0.088
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.0(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     219
_refine_ls_number_reflns         2904
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.116
_refine_ls_R_factor_all          0.1281
_refine_ls_R_factor_gt           0.1262
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1500P)^2^+4.0870P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3226
_refine_ls_wR_factor_ref         0.3242
_reflns_number_gt                2797
_reflns_number_total             2904
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d0sc04685j2.cif
_cod_data_source_block           20190409_sxs-8-13
_cod_database_code               1559111
_reflns_odcompleteness_completeness 99.83
_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, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O2-C17
 1.5 with sigma of 0.02
 O2-C17
 1.5 with sigma of 0.02
 C16-O2
 1.4 with sigma of 0.02
 C16-O1
 1.4 with sigma of 0.02
3.a Rotating group:
 N1(H1A,H1B)
3.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C17(H17A,H17B)
3.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C11(H11), C12(H12)
3.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C)
;
_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 1.893
_oxdiff_exptl_absorpt_empirical_full_min 0.356