Enantiodivergent α-Amino C-H Fluoroalkylation Catalyzed by Engineered Cytochrome P450s.
Zhang, Juner; Huang, Xiongyi; Zhang, Ruijie K.; Arnold, Frances H.; Journal of the American Chemical Society 141 (2019) 9798–9802; doi:10.1021/jacs.9b04344

data_4128277
_publ_section_title
;
 Enantiodivergent \a-Amino C-H Fluoroalkylation Catalyzed by Engineered
 Cytochrome P450s.
;
_journal_issue                   25
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9798
_journal_page_last               9802
_journal_paper_doi               10.1021/jacs.9b04344
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C12 H14 F3 N'
_chemical_formula_sum            'C12 H14 F3 N'
_chemical_formula_weight         229.24
_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
_audit_creation_date             2019-03-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506),
 SHELXL-2018/3, and manual edit
;
_cell_angle_alpha                90
_cell_angle_beta                 116.975(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.3312(11)
_cell_length_b                   17.574(2)
_cell_length_c                   8.3790(11)
_cell_measurement_reflns_used    9509
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      80.16
_cell_measurement_theta_min      5.03
_cell_volume                     1093.3(2)
_computing_cell_refinement       'SAINT V8.38A (Bruker-AXS, 2016)'
_computing_data_collection
'BIS V6.2.9/2018-03-16 & APEX3 v2018.7-2 (Bruker-AXS, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker-AXS, 2016)'
_computing_molecular_graphics    'DIAMOND 3 (Crystal Impact, 1999)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT-2014/5 (Sheldrick, 2013)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'CPAD Area Detector'
_diffrn_detector_area_resol_mean 7.69
_diffrn_detector_type            'Bruker PHOTON II'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'multilayer mirrors'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0463
_diffrn_reflns_av_unetI/netI     0.0198
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            50963
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         80.766
_diffrn_reflns_theta_min         5.033
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_current           1
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatec I\mS HB'
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.008
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7849
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1168 before and 0.0824 after correction. The Ratio of minimum to maximum transmission is 0.7849. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.393
_exptl_crystal_description       block
_exptl_crystal_F_000             480
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.213
_refine_diff_density_min         -0.189
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 2199 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(2)
_refine_ls_extinction_coef       0.0050(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     290
_refine_ls_number_reflns         4683
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0279
_refine_ls_R_factor_gt           0.0279
_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^)+(0.0341P)^2^+0.2776P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0705
_refine_ls_wR_factor_ref         0.0705
_reflns_Friedel_coverage         0.904
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.961
_reflns_number_gt                4669
_reflns_number_total             4683
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b04344_si_002.cif
_cod_data_source_block           v18648
_cod_original_cell_volume        1093.3(3)
_cod_database_code               4128277
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.864
_shelx_estimated_absorpt_t_min   0.766
_refine_ls_abs_structure_hooft   0.08(2)
_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:
 C10(H10), C10B(H10B)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C11(H11A,H11B), C7B(H7C,H7D), C8B(H8C,
 H8D), C9B(H9C,H9D), C11B(H11C,H11D)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C1B(H1B), C2B(H2B), C3B(H3B),
 C4B(H4B), C5B(H5B)
;
_shelx_res_checksum              57271
_shelx_hkl_checksum              14553
_olex2_submission_special_instructions 'No special instructions were received'