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_7135130
_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         '0.5(C22 H18 F N O3)'
_chemical_formula_sum            'C11 H9 F0.5 N0.5 O1.5'
_chemical_formula_weight         181.69
_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             2024-04-27
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-07-15 deposited with the CCDC.	2025-10-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.0170(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   7.34490(10)
_cell_length_b                   9.46510(10)
_cell_length_c                   25.5608(3)
_cell_measurement_reflns_used    15619
_cell_measurement_temperature    299.19(10)
_cell_measurement_theta_max      77.7720
_cell_measurement_theta_min      4.9820
_cell_volume                     1774.53(4)
_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 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      299.19(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.970
_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     58.00  83.00   0.50    0.27    --  108.07-140.00 112.00   50
  2  \w     62.00  89.00   0.50    0.07    --   50.49-140.00 112.00   54
  3  \w     89.00 115.00   0.50    0.27    --  108.07-130.00 -73.00   52
  4  \w     69.00 112.00   0.50    0.27    --  108.07-125.00 -90.00   86
  5  \w     38.00  73.00   0.50    0.07    --   50.49-130.00 -73.00   70
  6  \w     80.00 105.00   0.50    0.27    --  108.07 -99.00   0.00   50
  7  \w     38.00  84.00   0.50    0.27    --  108.07 -99.00 -30.00   92
  8  \w     53.00 106.00   0.50    0.27    --  108.07 -99.00 -90.00  106
  9  \w     77.00 103.00   0.50    0.27    --  108.07 -99.00-180.00   52
 10  \w     38.00  66.00   0.50    0.27    --  108.07 -99.00   0.00   56
 11  \w     77.00 112.00   0.50    0.27    --  108.07-125.00  30.00   70
 12  \w     38.00  94.00   0.50    0.27    --  108.07 -99.00  90.00  112
 13  \w     39.00  97.00   0.50    0.27    --  108.07 -99.00 120.00  116
 14  \w     38.00 104.00   0.50    0.27    --  108.07 -99.00 150.00  132
 15  \w     36.00  61.00   0.50    0.27    --  108.07 -57.00  90.00   50
 16  \w    -20.00   6.00   0.50    0.07    --   50.49 -19.00  30.00   52
 17  \w     -2.00  23.00   0.50    0.07    --   50.49 -19.00   0.00   50
 18  \w     39.00  65.00   0.50    0.27    --  108.07 -57.00-120.00   52
 19  \w     39.00  64.00   0.50    0.27    --  108.07 -57.00 -30.00   50
 20  \w    103.00 178.00   0.50    0.27    --  108.07  38.00  90.00  150
 21  \w    143.00 168.00   0.50    0.27    --  108.07  57.00 150.00   50
 22  \w    106.00 136.00   0.50    0.27    --  108.07  57.00 150.00   60
 23  \w    128.00 173.00   0.50    0.27    --  108.07 140.00 171.00   90
 24  \w     97.00 123.00   0.50    0.27    --  108.07 140.00 171.00   52
 25  \w    100.00 147.00   0.50    0.27    --  108.07 130.00  -1.00   94
 26  \w    101.00 132.00   0.50    0.27    --  108.07 125.00 -90.00   62
 27  \w    -26.00  23.00   0.50    0.07    --  -50.49  19.00 120.00   98
 28  \w    -83.00 -58.00   0.50    0.27    --  -90.00 140.00 171.00   50
 29  \w    -84.00 -59.00   0.50    0.07    --  -50.49 140.00 171.00   50
 30  \w    -81.00 -43.00   0.50    0.07    --  -50.49 130.00  -1.00   76
 31  \w    -82.00 -51.00   0.50    0.27    --  -90.00 130.00  -1.00   62
 32  \w    -50.00 -19.00   0.50    0.27    --  -90.00  57.00 -30.00   62
 33  \w    -66.00 -21.00   0.50    0.27    --  -90.00 125.00-120.00   90
 34  \w    -64.00 -20.00   0.50    0.27    --  -90.00  57.00-150.00   88
 35  \w   -158.00 -82.00   0.50    0.27    --  -90.00 -19.00 -30.00  152
 36  \w   -161.00 -83.00   0.50    0.27    --  -90.00 -38.00 -90.00  156
 37  \w   -121.00 -32.00   0.50    0.07    --  -50.49 -77.00-180.00  178
 38  \w   -140.00 -69.00   0.50    0.27    --  -90.00 -77.00-150.00  142
 39  \w   -159.00 -89.00   0.50    0.27    --  -90.00 -99.00-120.00  140
 40  \w   -139.00-114.00   0.50    0.27    --  -90.00-130.00 -73.00   50
 41  \w   -119.00 -94.00   0.50    0.07    --  -50.49-125.00 -60.00   50
 42  \w   -114.00 -85.00   0.50    0.07    --  -50.49-125.00 -90.00   58
 43  \w    -97.00 -70.00   0.50    0.07    --  -50.49-130.00 -73.00   54
 44  \w   -119.00 -63.00   0.50    0.07    --  -50.49-140.00 112.00  112
 45  \w   -126.00 -64.00   0.50    0.27    --  -90.00-140.00 112.00  124
;
_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      -0.1151932000
_diffrn_orient_matrix_UB_12      0.0164961000
_diffrn_orient_matrix_UB_13      0.0482743000
_diffrn_orient_matrix_UB_21      -0.1695862000
_diffrn_orient_matrix_UB_22      0.0316651000
_diffrn_orient_matrix_UB_23      -0.0361427000
_diffrn_orient_matrix_UB_31      -0.0457626000
_diffrn_orient_matrix_UB_32      -0.1588108000
_diffrn_orient_matrix_UB_33      -0.0021913000
_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  0.0579
_diffrn_reflns_av_unetI/netI     0.0397
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            23690
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.871
_diffrn_reflns_theta_min         3.463
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.805
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59485
_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_density_diffrn    1.360
_exptl_crystal_F_000             760
_refine_diff_density_max         0.288
_refine_diff_density_min         -0.170
_refine_diff_density_rms         0.042
_refine_ls_extinction_coef       0.0028(4)
_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   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     246
_refine_ls_number_reflns         3679
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0487
_refine_ls_R_factor_gt           0.0449
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0667P)^2^+0.3903P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1253
_refine_ls_wR_factor_ref         0.1289
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3285
_reflns_number_total             3679
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04004c2.cif
_cod_data_source_block           exp_8121_auto
_cod_depositor_comments
'Adding full bibliography for 7135129--7135130.cif.'
_cod_original_formula_sum        'C11 H9 F0.50 N0.50 O1.50'
_cod_database_code               7135130
_shelx_shelxl_version_number     2018/3
_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:
 C006(H006), C009(H009)
2.b Secondary CH2 refined with riding coordinates:
 C00F(H00A,H00B)
2.c Aromatic/amide H refined with riding coordinates:
 C00E(H00E), C00H(H00H), C00I(H00I), C00J(H00J), C00K(H00K), C00L(H00L),
 C00M(H00M), C00O(H00O), C00P(H00P), C00Q(H00Q), C00R(H00R)
2.d Idealised Me refined as rotating group:
 C00N(H00C,H00D,H00F)
;
_shelx_res_checksum              69771
_shelx_hkl_checksum              28409
_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 3.154
_oxdiff_exptl_absorpt_empirical_full_min 0.488