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_4128276
_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         'C14 H16 F5 N O'
_chemical_formula_sum            'C14 H16 F5 N O'
_chemical_formula_weight         309.28
_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                 98.627(7)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.7849(11)
_cell_length_b                   5.4108(8)
_cell_length_c                   14.8752(19)
_cell_measurement_reflns_used    9848
_cell_measurement_temperature    100
_cell_measurement_theta_max      79.05
_cell_measurement_theta_min      3.00
_cell_volume                     699.07(16)
_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
_diffrn_detector                 'CPAD Area Detector'
_diffrn_detector_area_resol_mean 7.69
_diffrn_detector_type            'Bruker PHOTON II'
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.967
_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  0.0414
_diffrn_reflns_av_unetI/netI     0.0219
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            22266
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.936
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         79.309
_diffrn_reflns_theta_min         3.005
_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    1.212
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.6450
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1210 before and 0.0849 after correction.
The Ratio of minimum to maximum transmission is 0.6450.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.469
_exptl_crystal_description       block
_exptl_crystal_F_000             320
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.213
_refine_diff_density_min         -0.137
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 1190 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.15(4)
_refine_ls_extinction_coef       0.0038(9)
_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   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     192
_refine_ls_number_reflns         2842
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0279
_refine_ls_R_factor_gt           0.0276
_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^)+(0.0283P)^2^+0.2093P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0694
_refine_ls_wR_factor_ref         0.0696
_reflns_Friedel_coverage         0.748
_reflns_Friedel_fraction_full    0.972
_reflns_Friedel_fraction_max     0.899
_reflns_number_gt                2809
_reflns_number_total             2842
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b04344_si_003.cif
_cod_data_source_block           v18651
_cod_database_code               4128276
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.868
_shelx_estimated_absorpt_t_min   0.760
_refine_ls_abs_structure_hooft   0.17(3)
_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:
 C11(H11)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C12(H12A,H12B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5)
2.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_shelx_res_checksum              89101
_shelx_hkl_checksum              14104
_olex2_submission_special_instructions 'No special instructions were received'