Highly Diastereo- and Enantioselective Synthesis of Trifluoromethyl-Substituted Cyclopropanes via Myoglobin-Catalyzed Transfer of Trifluoromethylcarbene.
Tinoco, Antonio; Steck, Viktoria; Tyagi, Vikas; Fasan, Rudi; Journal of the American Chemical Society 139 (2017) 5293–5296; doi:10.1021/jacs.7b00768

data_4126161
_publ_section_title
;
 Highly Diastereo- and Enantioselective Synthesis of
 Trifluoromethyl-Substituted Cyclopropanes via Myoglobin-Catalyzed
 Transfer of Trifluoromethylcarbene.
;
_journal_issue                   15
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5293
_journal_page_last               5296
_journal_paper_doi               10.1021/jacs.7b00768
_journal_volume                  139
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C10 H8 F3 N O2'
_chemical_formula_sum            'C10 H8 F3 N O2'
_chemical_formula_weight         231.17
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-01-06
_audit_creation_method
;
Olex2 1.2-ac21
(compiled 2015.09.16 svn.r134, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 110.999(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.0948(3)
_cell_length_b                   6.72581(17)
_cell_length_c                   9.5368(3)
_cell_measurement_reflns_used    8120
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.6550
_cell_measurement_theta_min      9.5270
_cell_volume                     484.74(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.7f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.7f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.7f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_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    -95.00 -12.00   0.50    7.00    --  -84.25 125.00  30.00  166
  2  \w     92.00 177.00   0.50    7.00    --  105.75  61.00-150.00  170
  3  \w     97.00 178.00   0.50    7.00    --  105.75  45.00 -90.00  162
  4  \w     97.00 178.00   0.50    7.00    --  105.75  45.00-120.00  162
  5  \w     85.00 178.00   0.50    7.00    --  105.75  77.00-180.00  186
  6  \w     98.00 178.00   0.50    7.00    --  105.75  15.00-180.00  160
  7  \w     98.00 178.00   0.50    7.00    --  105.75  30.00 -30.00  160
  8  \w     98.00 178.00   0.50    7.00    --  105.75  30.00   0.00  160
  9  \w     98.00 178.00   0.50    7.00    --  105.75  30.00  30.00  160
 10  \w     98.00 178.00   0.50    7.00    --  105.75  30.00 150.00  160
 11  \w    -67.00  13.00   0.50    3.00    --    5.92 -19.00   0.00  160
 12  \w     34.00  80.00   0.50    7.00    --  105.75 -45.00-150.00   92
 13  \w    -62.00 -12.00   0.50    7.00    --  -84.25  15.00-150.00  100
 14  \w    -86.00 -12.00   0.50    7.00    --  -84.25  45.00-180.00  148
 15  \w    -63.00 -12.00   0.50    7.00    --  -84.25  30.00  30.00  102
 16  \w    -86.00 -12.00   0.50    7.00    --  -84.25  45.00 -60.00  148
 17  \w    -66.00  14.00   0.50    3.00    --    5.92 -37.00 150.00  160
 18  \w    -67.00  13.00   0.50    3.00    --    5.92 -19.00-180.00  160
 19  \w     34.00  80.00   0.50    7.00    --  105.75 -45.00-120.00   92
 20  \w     34.00 127.00   0.50    7.00    --  105.75 -77.00  30.00  186
 21  \w     34.00 120.00   0.50    7.00    --  105.75 -61.00 150.00  172
 22  \w     98.00 178.00   0.50    7.00    --  105.75  30.00  90.00  160
 23  \w     -7.00  77.00   0.50    3.00    --    5.92  57.00  90.00  168
 24  \w     -2.00  78.00   0.50    3.00    --    5.92  37.00  30.00  160
 25  \w     -7.00  77.00   0.50    3.00    --    5.92  57.00 120.00  168
 26  \w     -7.00  77.00   0.50    3.00    --    5.92  57.00 -60.00  168
 27  \w    -26.00  66.00   0.50    3.00    --   -5.92  77.00   0.00  184
 28  \w    -26.00  66.00   0.50    3.00    --   -5.92  77.00-150.00  184
 29  \w     -1.00  79.00   0.50    3.00    --    5.92  19.00 -90.00  160
 30  \w     -2.00  78.00   0.50    3.00    --    5.92  37.00-180.00  160
 31  \w    -66.00  54.00   0.50    3.00    --    5.92   0.00-180.00  240
 32  \w   -156.00 -63.00   0.50    7.00    --  -84.25 -77.00  30.00  186
 33  \w   -156.00 -70.00   0.50    7.00    --  -84.25 -61.00 150.00  172
 34  \w   -156.00 -63.00   0.50    7.00    --  -84.25 -77.00 -30.00  186
 35  \w   -156.00 -75.00   0.50    7.00    --  -84.25 -45.00 -90.00  162
 36  \w   -156.00 -63.00   0.50    7.00    --  -84.25 -77.00-150.00  186
 37  \w   -156.00 -63.00   0.50    7.00    --  -84.25 -77.00-120.00  186
 38  \w   -156.00 -63.00   0.50    7.00    --  -84.25 -77.00 -90.00  186
 39  \w   -156.00 -63.00   0.50    7.00    --  -84.25 -77.00   0.00  186
 40  \w   -156.00 -75.00   0.50    7.00    --  -84.25 -45.00  30.00  162
 41  \w   -156.00 -63.00   0.50    7.00    --  -84.25 -77.00  90.00  186
 42  \w   -156.00 -70.00   0.50    7.00    --  -84.25 -61.00 120.00  172
 43  \w   -156.00 -63.00   0.50    7.00    --  -84.25 -77.00 150.00  186
 44  \w   -156.00 -75.00   0.50    7.00    --  -84.25 -45.00 150.00  162
 45  \w   -156.00 -63.00   0.50    7.00    --  -84.25 -77.00  60.00  186
 46  \w   -156.00 -75.00   0.50    7.00    --  -84.25 -45.00  90.00  162
 47  \w   -155.00 -65.00   0.50    7.00    --  -84.25 -73.00 -24.00  180
 48  \w   -156.00 -63.00   0.50    7.00    --  -84.25 -77.00 -60.00  186
 49  \w   -156.00 -75.00   0.50    7.00    --  -84.25 -45.00 -30.00  162
 50  \w    -78.00   2.00   0.50    3.00    --   -5.92 -37.00 150.00  160
 51  \w    -77.00   7.00   0.50    3.00    --   -5.92 -57.00 150.00  168
 52  \w   -156.00 -70.00   0.50    7.00    --  -84.25 -61.00 -60.00  172
 53  \w   -156.00 -70.00   0.50    7.00    --  -84.25 -61.00 -90.00  172
 54  \w   -156.00 -70.00   0.50    7.00    --  -84.25 -61.00-120.00  172
 55  \w   -156.00 -76.00   0.50    7.00    --  -84.25 -30.00-180.00  160
 56  \w   -156.00 -63.00   0.50    7.00    --  -84.25 -77.00 120.00  186
 57  \w   -156.00 -63.00   0.50    7.00    --  -84.25 -77.00-180.00  186
 58  \w   -156.00 -76.00   0.50    7.00    --  -84.25 -30.00 150.00  160
 59  \w     34.00 120.00   0.50    7.00    --  105.75-125.00   0.00  172
 60  \w     35.00 108.00   0.50    7.00    --  105.75 -94.00 150.00  146
 61  \w     35.00 108.00   0.50    7.00    --  105.75 -94.00 -30.00  146
 62  \w     34.00 120.00   0.50    7.00    --  105.75-125.00-120.00  172
 63  \w     35.00 108.00   0.50    7.00    --  105.75 -94.00  30.00  146
 64  \w     35.00 108.00   0.50    7.00    --  105.75 -94.00-150.00  146
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1196310000
_diffrn_orient_matrix_UB_12      0.1555213000
_diffrn_orient_matrix_UB_13      0.1077722000
_diffrn_orient_matrix_UB_21      0.1217247000
_diffrn_orient_matrix_UB_22      -0.1674956000
_diffrn_orient_matrix_UB_23      0.0904361000
_diffrn_orient_matrix_UB_31      0.1115276000
_diffrn_orient_matrix_UB_32      0.0160662000
_diffrn_orient_matrix_UB_33      -0.1006970000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0722
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            16801
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        66.598
_diffrn_reflns_theta_max         66.598
_diffrn_reflns_theta_min         9.044
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.312
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.868
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.7f (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_colour_primary    colourless
_exptl_crystal_density_diffrn    1.584
_exptl_crystal_description       plate
_exptl_crystal_F_000             236
_exptl_crystal_size_max          0.104
_exptl_crystal_size_mid          0.081
_exptl_crystal_size_min          0.055
_refine_diff_density_max         0.169
_refine_diff_density_min         -0.198
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 714 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.03(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     145
_refine_ls_number_reflns         1694
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0303
_refine_ls_R_factor_gt           0.0294
_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^)+(0.0540P)^2^+0.0469P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0791
_refine_ls_wR_factor_ref         0.0796
_reflns_Friedel_coverage         0.829
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                1645
_reflns_number_total             1694
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b00768_si_002.cif
_cod_data_source_block           rochester_as
_cod_database_code               4126161
_chemical_oxdiff_formula         'C10 H8 F3 N O2'
_diffrn_oxdiff_ac3_digest_frames
;
01b08f904702f3a328193bdf910fb3fc171057685ef
;
_diffrn_oxdiff_ac3_digest_hkl
;
010a8a395086b1f8b7c3ad0d181818d9baf840
;
_reflns_odcompleteness_completeness 99.25
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C2(H2), C4(H4)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C10(H10), C6(H6), C9(H9)
;
_shelx_res_checksum              69629
_shelx_hkl_checksum              90562
_shelx_shelxl_version_number     2014/7
_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 2.311
_oxdiff_exptl_absorpt_empirical_full_min 0.271