Chemo-enzymatic synthesis of chiral 3-substituted tetrahydroquinolines by a sequential biocatalytic cascade and Buchwald–Hartwig cyclization
Xu, Zefei; Feng, Jinhui; Yao, Peiyuan; Wu, Qiaqing; Zhu, Dunming; Green Chemistry 25 (2023) 4667–4673; doi:10.1039/D3GC00047H

data_7246457
_publ_section_title
;
 Chemo-enzymatic synthesis of chiral 3-substituted tetrahydroquinolines by
 a sequential biocatalytic cascade and Buchwald--Hartwig cyclization
;
_journal_issue                   12
_journal_name_full               'Green Chemistry'
_journal_page_first              4667
_journal_page_last               4673
_journal_paper_doi               10.1039/D3GC00047H
_journal_volume                  25
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C13 H18 Br F N, Cl'
_chemical_formula_sum            'C13 H18 Br Cl F N'
_chemical_formula_weight         322.64
_chemical_name_systematic
'(S)-N-(3-(2-bromo-5-fluorophenyl)-2-methylpropyl)prop-2-en-1-amine hydrochloride'
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-02-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-02-17 deposited with the CCDC.	2023-03-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.954(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   4.83350(10)
_cell_length_b                   26.0950(6)
_cell_length_c                   11.3444(3)
_cell_measurement_reflns_used    17331
_cell_measurement_temperature    113(2)
_cell_measurement_theta_max      34.6170
_cell_measurement_theta_min      1.9940
_cell_volume                     1430.67(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      113.15
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.993
_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   -110.00  70.00   0.50    2.00    --  -20.00   0.00  90.00  360
  2  \w   -110.00   7.00   0.50    2.00    --  -20.00 -70.00 180.00  234
  3  \w   -110.00   7.00   0.50    2.00    --  -20.00 -70.00   0.00  234
  4  \w   -110.00   7.00   0.50    2.00    --  -20.00 -70.00  90.00  234
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  'Rigaku Saturn 944'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0149038000
_diffrn_orient_matrix_UB_12      0.0269507000
_diffrn_orient_matrix_UB_13      0.0050336000
_diffrn_orient_matrix_UB_21      0.0000876000
_diffrn_orient_matrix_UB_22      -0.0021507000
_diffrn_orient_matrix_UB_23      0.0623208000
_diffrn_orient_matrix_UB_31      0.1460225000
_diffrn_orient_matrix_UB_32      -0.0027447000
_diffrn_orient_matrix_UB_33      0.0005628000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0167
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            11088
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.697
_diffrn_reflns_theta_min         1.561
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.050
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51502
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
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    1.498
_exptl_crystal_description       prism
_exptl_crystal_F_000             656
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.866
_refine_diff_density_min         -0.804
_refine_diff_density_rms         0.170
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.004(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     311
_refine_ls_number_reflns         11088
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0531
_refine_ls_R_factor_gt           0.0491
_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^)+(0.1259P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1436
_refine_ls_wR_factor_ref         0.1472
_reflns_Friedel_coverage         0.922
_reflns_Friedel_fraction_full    0.979
_reflns_Friedel_fraction_max     0.956
_reflns_number_gt                10181
_reflns_number_total             11088
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.9842\% 
around [1.00 0.00 -0.04] (reciprocal) or [1.00 0.00 -0.00] (direct)
;
_cod_data_source_file            d3gc00047h2.cif
_cod_data_source_block           r20230217e_twin1_hklf5
_cod_depositor_comments
'Adding full bibliography for 7246452--7246458.cif.'
_cod_database_code               7246457
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C13 H18 Br1 Cl1 F1 N1'
_shelx_estimated_absorpt_t_max   0.641
_shelx_estimated_absorpt_t_min   0.390
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.47(5)
 0.37(2) 0.16(5)
2. 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
3.a Ternary CH refined with riding coordinates:
 C2(H2), C15(H15)
3.b Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), C1(H1C,H1D), C3(H3A,H3B), C11(H11A,H11B), N2(H2A,H2B), C14(H14A,
 H14B), C16(H16A,H16B), C24(H24A,H24B)
3.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C9(H9), C12(H12), C19(H19), C20(H20), C22(H22), C25(H25)
3.d X=CH2 refined with riding coordinates:
 C13(H13A,H13B), C26(H26A,H26B)
3.e Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              47804
_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 1.392
_oxdiff_exptl_absorpt_empirical_full_min 0.646
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2