Rh(III)-catalyzed C-H activation/β-F elimination/Michael addition: diastereoselective access to dihydroisoquinolinones featuring β-amino α-fluorocarbonyl motif.
Lin, Wei; Luo, Zhenli; Zhu, Huixuan; Hu, Jinhui; Xiong, Zhuang; Wu, Jia-Qiang; Chemical communications (Cambridge, England) 61 (2025) 18709–18712; doi:10.1039/d5cc04004c

data_7135129
_publ_section_title
;
 Rh(III)-catalyzed C-H activation/&#x3b2;-F elimination/Michael addition:
 diastereoselective access to dihydroisoquinolinones featuring
 &#x3b2;-amino &#x3b1;-fluorocarbonyl motif.
;
_journal_issue                   94
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              18709
_journal_page_last               18712
_journal_paper_doi               10.1039/d5cc04004c
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C22 H18 F N O3'
_chemical_formula_sum            'C22 H18 F N O3'
_chemical_formula_weight         363.37
_chemical_name_systematic
3-(1-fluoro-2-(naphthalen-2-yl)-2-oxoethyl)-2-methoxy-3,4-dihydroisoquinolin-1(2H)-one
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-04-21
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-04-21 deposited with the CCDC.	2025-10-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.376(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.0201(3)
_cell_length_b                   7.3436(2)
_cell_length_c                   21.6386(6)
_cell_measurement_reflns_used    6370
_cell_measurement_temperature    213(20)
_cell_measurement_theta_max      77.3430
_cell_measurement_theta_min      4.3440
_cell_volume                     1746.05(8)
_computing_cell_refinement       'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      213(20)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.938
_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     59.00  98.00   0.50    1.34    --  108.07 -99.00  90.00   78
  2  \w     76.00 102.00   0.50    1.34    --  108.07 -99.00  60.00   52
  3  \w     48.00 106.00   0.50    1.34    --  108.07 -99.00   0.00  116
  4  \w     57.00 102.00   0.50    1.34    --  108.07 -99.00-120.00   90
  5  \w     58.00  83.00   0.50    1.34    --  108.07 -77.00-150.00   50
  6  \w     38.00  65.00   0.50    1.34    --  108.07 -57.00-120.00   54
  7  \w     38.00  63.00   0.50    1.34    --  108.07 -57.00 -60.00   50
  8  \w     36.00  64.00   0.50    1.34    --  108.07 -57.00 -90.00   56
  9  \w     36.00  66.00   0.50    1.34    --  108.07 -57.00  30.00   60
 10  \w     36.00  62.00   0.50    1.34    --  108.07 -57.00  90.00   52
 11  \w     40.00  66.00   0.50    1.34    --  108.07 -57.00 120.00   52
 12  \w     37.00  65.00   0.50    1.34    --  108.07 -57.00 150.00   56
 13  \w    -11.00  26.00   0.50    0.34    --   50.36 -18.00 105.00   74
 14  \w     -2.00  26.00   0.50    0.34    --   50.36 -19.00   0.00   56
 15  \w     83.00 108.00   0.50    0.34    --   50.36  18.00 -86.00   50
 16  \w    107.00 178.00   0.50    1.34    --  108.07  38.00-180.00  142
 17  \w    101.00 169.00   0.50    1.34    --  108.07  18.00 -86.00  136
 18  \w    -50.00 -19.00   0.50    1.34    --  -90.00  57.00-180.00   62
 19  \w    -53.00 -18.00   0.50    1.34    --  -90.00  57.00-120.00   70
 20  \w    -24.00  23.00   0.50    0.34    --  -50.36  18.00 -86.00   94
 21  \w    -26.00  21.00   0.50    0.34    --  -50.36  19.00 -30.00   94
 22  \w    -24.00  13.00   0.50    0.34    --  -50.36  19.00  60.00   74
 23  \w   -105.00 -43.00   0.50    0.34    --  -50.36 -18.00 105.00  124
 24  \w   -134.00 -90.00   0.50    1.34    --  -90.00 -18.00 105.00   88
 25  \w    -71.00 -31.00   0.50    1.34    --  -90.00 125.00 -30.00   80
 26  \w   -109.00 -84.00   0.50    1.34    --  -90.00 -38.00-150.00   50
;
_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      -0.1140603000
_diffrn_orient_matrix_UB_12      0.0517496000
_diffrn_orient_matrix_UB_13      0.0330809000
_diffrn_orient_matrix_UB_21      0.0774095000
_diffrn_orient_matrix_UB_22      0.0088239000
_diffrn_orient_matrix_UB_23      0.0622751000
_diffrn_orient_matrix_UB_31      0.0256435000
_diffrn_orient_matrix_UB_32      0.2031313000
_diffrn_orient_matrix_UB_33      -0.0111404000
_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  0.0288
_diffrn_reflns_av_unetI/netI     0.0276
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.938
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -4
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            11495
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.632
_diffrn_reflns_theta_min         4.098
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.818
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74983
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.94a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.382
_exptl_crystal_description       plate
_exptl_crystal_F_000             760
_exptl_crystal_preparation       no
_exptl_crystal_recrystallization_method 'Vapour deposition'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.257
_refine_diff_density_min         -0.214
_refine_diff_density_rms         0.039
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     245
_refine_ls_number_reflns         3518
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0469
_refine_ls_R_factor_gt           0.0391
_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^)+(0.0559P)^2^+0.4179P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1035
_refine_ls_wR_factor_ref         0.1090
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2967
_reflns_number_total             3518
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04004c2.cif
_cod_data_source_block           exp_7897_auto
_cod_depositor_comments
'Adding full bibliography for 7135129--7135130.cif.'
_cod_database_code               7135129
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.992
_shelx_estimated_absorpt_t_min   0.853
_reflns_odcompleteness_completeness 99.70
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C9(H9), C11(H11)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B)
2.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C3(H3), C21(H21), C22(H22), C6(H6), C5(H5), C16(H16), C4(H4),
 C19(H19), C18(H18), C17(H17)
2.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C)
;
_shelx_res_checksum              61163
_shelx_hkl_checksum              58760
_olex2_exptl_crystal_mounting_method no
_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 1.528
_oxdiff_exptl_absorpt_empirical_full_min 0.775