Diastereoselective synthesis of chiral 3-substituted isoindolinones <i>via</i> rhodium(III)-catalyzed oxidative C-H olefination/annulation.
Li, Xue-Hong; Gong, Jun-Fang; Song, Mao-Ping; Organic & biomolecular chemistry 19 (2021) 5876–5887; doi:10.1039/d1ob00656h

data_7158118
_publ_section_title
;
 Diastereoselective synthesis of chiral 3-substituted isoindolinones
 <i>via</i> rhodium(III)-catalyzed oxidative C-H olefination/annulation.
;
_journal_issue                   26
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              5876
_journal_page_last               5887
_journal_paper_doi               10.1039/d1ob00656h
_journal_volume                  19
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C15 H19 N O4 S'
_chemical_formula_sum            'C15 H19 N O4 S'
_chemical_formula_weight         309.37
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2020-09-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-11-26 deposited with the CCDC.	2021-06-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.6665(5)
_cell_length_b                   9.0914(5)
_cell_length_c                   20.0289(10)
_cell_measurement_reflns_used    1974
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.7600
_cell_measurement_theta_min      4.4110
_cell_volume                     1578.09(15)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -80.00 -53.00   1.00    1.00    --  -33.50 -77.00-180.00   27
  2  \w      6.00  49.00   1.00    1.00    --   36.47 -57.00-180.00   43
  3  \w     70.00 106.00   1.00    1.00    --   36.47 178.00-180.00   36
  4  \w     11.00  36.00   1.00    1.00    --   36.47  77.00 150.00   25
  5  \w     60.00 107.00   1.00    1.00    --   36.47 178.00  30.00   47
  6  \w     65.00  90.00   1.00    1.00    --   36.47 178.00-150.00   25
  7  \w     46.00 102.00   1.00    1.00    --   36.47  77.00 150.00   56
  8  \w     52.00 105.00   1.00    4.00    --  108.00 -94.00 120.00   53
  9  \w    103.00 145.00   1.00    4.00    --  108.00  97.00 114.00   42
 10  \w     88.00 152.00   1.00    4.00    --  108.00  45.00  90.00   64
 11  \w     39.00  99.00   1.00    4.00    --  108.00-111.00   0.00   60
 12  \w     71.00 153.00   1.00    4.00    --  108.00  15.00-120.00   82
 13  \w    -61.00 -33.00   1.00    1.00    --  -33.50 178.00 -90.00   28
 14  \w    -30.00  12.00   1.00    1.00    --   36.47 -57.00  30.00   42
 15  \w     57.00  82.00   1.00    1.00    --   36.47 178.00   0.00   25
 16  \w     18.00  44.00   1.00    1.00    --   36.47 -57.00  30.00   26
 17  \w     99.00 125.00   1.00    2.50    --  108.00 -61.00 -30.00   26
 18  \w     71.00 107.00   1.00    2.50    --  108.00 -94.00 -90.00   36
 19  \w    113.00 139.00   1.00    2.50    --  108.00 111.00 -60.00   26
 20  \w     48.00  84.00   1.00    2.50    --  108.00 -61.00 -30.00   36
 21  \w     39.00  95.00   1.00    2.50    --  108.00   0.00   0.00   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1569899000
_diffrn_orient_matrix_UB_12      0.0794348000
_diffrn_orient_matrix_UB_13      0.0014336000
_diffrn_orient_matrix_UB_21      0.0757308000
_diffrn_orient_matrix_UB_22      0.1385241000
_diffrn_orient_matrix_UB_23      -0.0298430000
_diffrn_orient_matrix_UB_31      -0.0349874000
_diffrn_orient_matrix_UB_32      -0.0567028000
_diffrn_orient_matrix_UB_33      -0.0708692000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0316
_diffrn_reflns_av_unetI/netI     0.0434
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            5764
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.047
_diffrn_reflns_theta_max         67.047
_diffrn_reflns_theta_min         4.415
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.957
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77696
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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    1.302
_exptl_crystal_description       block
_exptl_crystal_F_000             656
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.178
_refine_diff_density_min         -0.245
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 904 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     207
_refine_ls_number_reflns         2812
_refine_ls_number_restraints     49
_refine_ls_restrained_S_all      1.326
_refine_ls_R_factor_all          0.0515
_refine_ls_R_factor_gt           0.0447
_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^)+(0.0568P)^2^+0.0408P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1087
_refine_ls_wR_factor_ref         0.1158
_reflns_Friedel_coverage         0.717
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                2475
_reflns_number_total             2812
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ob00656h2.cif
_cod_data_source_block           202009190
_cod_depositor_comments
'Adding full bibliography for 7158117--7158118.cif.'
_cod_database_code               7158118
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C30H30O2N2S1
_chemical_oxdiff_usercomment     r
_shelx_estimated_absorpt_t_max   0.828
_shelx_estimated_absorpt_t_min   0.745
_reflns_odcompleteness_completeness 99.94
_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. Restrained distances
 C13A-C14A
 2.2 with sigma of 0.02
 C15-C13 \\sim C15-C14 \\sim C13-C14 \\sim C14A-C13A \\sim C14A-C15A \\sim
C13A-C15A
 with sigma of 0.04
 C12-S1 \\sim C12-C15 \\sim C12-C13 \\sim C12-C14 \\sim C12-C14A \\sim C12-C13A
\\sim C12-C15A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C14A) \\sim Ueq, Uanis(C14) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C14) = Uanis(C14A)
Uanis(C13) = Uanis(C13A)
Uanis(C15) = Uanis(C15A)
4. Others
 Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C14A)=Sof(H14D)=Sof(H14E)=
 Sof(H14F)=Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=1-FVAR(1)
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C2(H2)
5.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B)
5.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8)
5.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C13A(H13D,H13E,H13F), C14(H14A,H14B,
 H14C), C14A(H14D,H14E,H14F), C15(H15A,H15B,H15C), C15A(H15D,H15E,H15F)
;
_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 1.751
_oxdiff_exptl_absorpt_empirical_full_min 0.862