Enantioselective C-H Functionalization-Addition Sequence Delivers Densely Substituted 3-Azabicyclo[3.1.0]hexanes.
Pedroni, Julia; Cramer, Nicolai; Journal of the American Chemical Society 139 (2017) 12398–12401; doi:10.1021/jacs.7b07024

data_4131581
_publ_section_title
;
 Enantioselective C-H Functionalization-Addition Sequence Delivers Densely
 Substituted 3-Azabicyclo[3.1.0]hexanes.
;
_journal_issue                   36
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              12398
_journal_page_last               12401
_journal_paper_doi               10.1021/jacs.7b07024
_journal_volume                  139
_journal_year                    2017
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C14 H17 F3 N O, Cl'
_chemical_formula_sum            'C14 H17 Cl F3 N O'
_chemical_formula_weight         307.73
_space_group_crystal_system      tetragonal
_space_group_IT_number           96
_space_group_name_Hall           'P 4nw 2abw'
_space_group_name_H-M_alt        'P 43 21 2'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2016/6
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.12744(5)
_cell_length_b                   10.12744(5)
_cell_length_c                   28.8870(3)
_cell_measurement_reflns_used    33178
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      75.6030
_cell_measurement_theta_min      3.0630
_cell_volume                     2962.80(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'CIFTAB (Sheldrick, 2016)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    132.00 158.00   1.00    1.01    --  111.85  61.00 120.00   26
  2  \w    114.00 148.00   1.00    1.00    --   74.00  77.00  97.42   34
  3  \w    108.00 134.00   1.00    1.01    --  111.85  77.00  30.00   26
  4  \w    113.00 178.00   1.00    1.01    --  111.85  77.00   0.00   65
  5  \w    136.00 169.00   1.00    1.01    --  111.85 125.00  60.00   33
  6  \w    103.00 141.00   1.00    1.00    --   66.00  77.00 136.75   38
  7  \w    100.00 140.00   1.00    1.00    --   66.00  77.00  62.15   40
  8  \w     97.00 123.00   1.00    1.00    --   66.00  77.00  19.78   26
  9  \w     99.00 146.00   1.00    1.00    --   70.00  77.00 -22.56   47
 10  \w    122.00 178.00   1.00    1.01    --  111.85  77.00 -90.00   56
 11  \w    113.00 142.00   1.00    1.00    --   74.00  76.00-143.19   29
 12  \w    103.00 130.00   1.00    1.00    --   70.00  76.00-179.08   27
 13  \w    112.00 178.00   1.00    1.01    --  111.85  77.00-120.00   66
 14  \w     92.00 147.00   1.00    1.00    --   74.00  77.00 -70.97   55
 15  \w     83.00 176.00   1.00    1.01    --  111.85  61.00  60.00   93
 16  \w     83.00 110.00   1.00    1.01    --  111.85  61.00 120.00   27
 17  \w     85.00 159.00   1.00    1.01    --  111.85  61.00 150.00   74
 18  \w     80.00 105.00   1.00    1.01    --  111.85  77.00  30.00   25
 19  \w     83.00 110.00   1.00    1.01    --  111.85  61.00  30.00   27
 20  \w     79.00 174.00   1.00    1.01    --  111.85  77.00 -30.00   95
 21  \w     85.00 110.00   1.00    1.01    --  111.85  61.00-180.00   25
 22  \w     79.00 105.00   1.00    1.01    --  111.85  77.00-120.00   26
 23  \w     79.00 167.00   1.00    1.01    --  111.85  77.00-150.00   88
 24  \w     83.00 118.00   1.00    1.01    --  111.85  61.00 -60.00   35
 25  \w     83.00 109.00   1.00    1.01    --  111.85  61.00-120.00   26
 26  \w     83.00 109.00   1.00    1.01    --  111.85  61.00 -90.00   26
 27  \w     79.00 104.00   1.00    1.01    --  111.85  77.00 -90.00   25
 28  \w     79.00 146.00   1.00    1.01    --  111.85  77.00 -60.00   67
 29  \w     80.00 169.00   1.00    1.01    --  111.85  77.00-180.00   89
 30  \w     79.00 104.00   1.00    1.01    --  111.85  77.00   0.00   25
 31  \w     79.00 105.00   1.00    1.01    --  111.85  77.00  60.00   26
 32  \w     79.00 177.00   1.00    1.01    --  111.85  77.00  90.00   98
 33  \w     82.00 108.00   1.00    1.01    --  111.85  77.00 150.00   26
 34  \w     79.00 105.00   1.00    1.01    --  111.85  77.00 120.00   26
 35  \w     84.00 109.00   1.00    1.01    --  111.85  61.00  90.00   25
 36  \w     58.00  89.00   1.00    1.01    --   90.00  75.00  -1.51   31
 37  \w     45.00  72.00   1.00    1.00    --   40.91  57.00   0.00   27
 38  \w     37.00  68.00   1.00    1.00    --   70.00  77.00 -22.56   31
 39  \w     42.00  68.00   1.00    1.00    --   74.00  77.00 -70.97   26
 40  \w     37.00  63.00   1.00    1.00    --   70.00  77.00 -98.45   26
 41  \w     42.00  86.00   1.00    1.00    --   74.00  76.00-143.19   44
 42  \w     38.00  65.00   1.00    1.00    --   70.00  76.00-179.08   27
 43  \w     20.00  46.00   1.00    1.00    --   54.00  81.00-124.26   26
 44  \w     11.00  36.00   1.00    1.00    --   46.00  84.00-133.19   25
 45  \w     21.00  46.00   1.00    1.00    --   54.00  79.00 -54.08   25
 46  \w     21.00  47.00   1.00    1.00    --   54.00  79.00  -2.26   26
 47  \w     34.00  60.00   1.00    1.00    --   66.00  77.00  19.78   26
 48  \w     33.00  64.00   1.00    1.00    --   66.00  77.00  62.15   31
 49  \w     41.00  72.00   1.00    1.00    --   74.00  77.00  97.42   31
 50  \w     33.00  65.00   1.00    1.00    --   66.00  77.00 136.75   32
 51  \w     21.00  46.00   1.00    1.00    --   54.00  79.00 127.02   25
 52  \w     11.00  36.00   1.00    1.00    --   46.00  84.00  47.27   25
 53  \w     15.00  43.00   1.00    1.00    --   40.91  57.00   0.00   28
 54  \w     13.00  38.00   1.00    1.00    --   46.00  79.00 -32.59   25
 55  \w      2.00  32.00   1.00    1.00    --   38.00  87.00 160.69   30
 56  \w     45.00 109.00   1.00    1.01    --  111.85 -94.00  90.00   64
 57  \w     44.00 120.00   1.00    1.01    --  111.85-125.00  30.00   76
 58  \w     39.00 120.00   1.00    1.01    --  111.85-125.00 -60.00   81
 59  \w     36.00  94.00   1.00    1.01    --  111.85 -94.00-180.00   58
 60  \w     23.00  90.00   1.00    1.00    --   40.91-125.00 -90.00   67
 61  \w     23.00  82.00   1.00    1.00    --   40.91-125.00  60.00   59
 62  \w     23.00  82.00   1.00    1.00    --   40.91-125.00 150.00   59
 63  \w     29.00  87.00   1.00    1.01    --  111.85 -94.00  30.00   58
 64  \w   -109.00 -17.00   1.00    1.00    --  -40.91 -37.00 123.00   92
 65  \w   -111.00 -19.00   1.00    1.00    --  -40.91 -38.00  30.00   92
 66  \w   -114.00 -17.00   1.00    1.00    --  -40.91 -43.00-123.89   97
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0414
_diffrn_reflns_av_unetI/netI     0.0128
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            52480
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.011
_diffrn_reflns_theta_min         4.627
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.560
_exptl_absorpt_correction_T_max  0.740
_exptl_absorpt_correction_T_min  0.391
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model.
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.380
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1280
_exptl_crystal_size_max          0.574
_exptl_crystal_size_mid          0.228
_exptl_crystal_size_min          0.157
_refine_diff_density_max         0.224
_refine_diff_density_min         -0.141
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 1198 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.001(3)
_refine_ls_extinction_coef       0.00029(10)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_parameters     250
_refine_ls_number_reflns         3096
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.0203
_refine_ls_R_factor_gt           0.0199
_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^)+(0.0287P)^2^+0.5211P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0533
_refine_ls_wR_factor_ref         0.0536
_reflns_Friedel_coverage         0.652
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                3054
_reflns_number_total             3096
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07024_si_002.cif
_cod_data_source_block           shelx
_cod_database_code               4131581
_shelx_shelxl_version_number     2016/6
_shelx_res_checksum              20250
_shelx_hkl_checksum              30595