Rh(i)-catalysed imine-directed C–H functionalization via the oxidative [3 + 2] cycloaddition of benzylamine derivatives with maleimides
Das, Amrita; Chatani, Naoto; Chemical Communications  (2022) –; doi:10.1039/D1CC06622F

data_7129498
_publ_section_title
;
 Rh(i)-catalysed imine-directed C--H functionalization via the oxidative
 [3 + 2] cycloaddition of benzylamine derivatives with maleimides
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC06622F
_journal_year                    2022
_chemical_formula_moiety         'C16 H13 N3 O2 S'
_chemical_formula_sum            'C16 H13 N3 O2 S'
_chemical_formula_weight         311.35
_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             2021-08-30
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.02.24 svn.r3390 for Rigaku Oxford Diffraction, GUI svn.r5318)
;
_audit_update_record
;
2021-11-11 deposited with the CCDC.	2021-12-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.056(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.7589(2)
_cell_length_b                   7.74990(10)
_cell_length_c                   16.8477(3)
_cell_measurement_reflns_used    7390
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      74.1190
_cell_measurement_theta_min      4.5440
_cell_volume                     1383.19(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.43a (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_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     13.00 116.00   0.50    0.13    --   42.80  80.00   1.00  206
  2  \w     74.00  99.00   0.50    0.53    --   76.50  80.00   1.00   50
  3  \w     71.00 114.00   0.50    0.13    --   42.80 125.00  30.00   86
  4  \w     -7.00  22.00   0.50    0.13    --   42.80 -80.00-121.00   58
  5  \w     44.00  70.00   0.50    0.13    --   42.80 -80.00-121.00   52
  6  \w     30.00  55.00   0.50    0.53    --   76.50 -80.00-121.00   50
  7  \w    -54.00 -14.00   0.50    0.13    --  -42.80 -80.00-121.00   80
  8  \w   -105.00 -76.00   0.50    0.53    -- -106.00 -80.00-121.00   58
  9  \w   -117.00 -92.00   0.50    0.53    -- -106.00 -37.00 -60.00   50
 10  \w   -109.00 -76.00   0.50    0.53    -- -106.00 -19.00 -90.00   66
 11  \w    -88.00 -55.00   0.50    0.53    -- -106.00  57.00   0.00   66
 12  \w    -67.00 -42.00   0.50    0.53    -- -106.00  77.00  30.00   50
 13  \w    -78.00 -46.00   0.50    0.53    -- -106.00  57.00 -30.00   64
 14  \w    -84.00 -34.00   0.50    0.53    -- -106.00  77.00 -60.00  100
 15  \w    -82.00 -56.00   0.50    0.53    -- -106.00  77.00   0.00   52
 16  \w   -108.00 -83.00   0.50    0.53    -- -106.00  80.00   1.00   50
 17  \w   -103.00 -77.00   0.50    0.53    -- -106.00  37.00   0.00   52
 18  \w   -128.00 -96.00   0.50    0.53    -- -106.00  57.00   0.00   64
 19  \w   -128.00 -33.00   0.50    0.53    -- -106.00  77.00  60.00  190
 20  \w    -74.00 -45.00   0.50    0.53    -- -106.00 125.00 150.00   58
 21  \w   -115.00 -87.00   0.50    0.53    -- -106.00 125.00 150.00   56
 22  \w   -117.00 -89.00   0.50    0.53    -- -106.00 125.00  60.00   56
 23  \w    -92.00 -48.00   0.50    0.13    --  -42.80 125.00 -30.00   88
 24  \w   -112.00 -82.00   0.50    0.53    -- -106.00 125.00-120.00   60
 25  \w   -131.00 -50.00   0.50    0.53    -- -106.00  77.00-180.00  162
 26  \w   -157.00-131.00   0.50    0.53    -- -106.00 -19.00 -90.00   52
 27  \w   -165.00 -83.00   0.50    0.53    -- -106.00 -57.00-120.00  164
 28  \w   -128.00-103.00   0.50    0.53    -- -106.00 -77.00 -60.00   50
 29  \w   -116.00 -70.00   0.50    0.13    --  -42.80-125.00   0.00   92
 30  \w   -134.00 -78.00   0.50    0.53    -- -106.00 -77.00  90.00  112
 31  \w   -109.00 -83.00   0.50    0.53    -- -106.00 -77.00 150.00   52
 32  \w   -129.00-102.00   0.50    0.53    -- -106.00 -99.00  90.00   54
 33  \w   -161.00 -86.00   0.50    0.53    -- -106.00 -37.00  90.00  150
 34  \w   -172.00-147.00   0.50    0.53    -- -106.00 -77.00  90.00   50
 35  \w   -173.00-148.00   0.50    0.53    -- -106.00 -57.00 150.00   50
 36  \w   -177.00-117.00   0.50    0.53    -- -106.00 -80.00-121.00  120
 37  \w   -176.00-126.00   0.50    0.53    -- -106.00 -77.00-150.00  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0856731000
_diffrn_orient_matrix_UB_12      -0.0844033000
_diffrn_orient_matrix_UB_13      -0.0724304000
_diffrn_orient_matrix_UB_21      -0.0953905000
_diffrn_orient_matrix_UB_22      0.1488433000
_diffrn_orient_matrix_UB_23      -0.0015301000
_diffrn_orient_matrix_UB_31      0.0686916000
_diffrn_orient_matrix_UB_32      0.1012264000
_diffrn_orient_matrix_UB_33      -0.0580592000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0413
_diffrn_reflns_av_unetI/netI     0.0366
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            12816
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.282
_diffrn_reflns_theta_min         4.543
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.182
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63973
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.43a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear Yellow'
_exptl_crystal_density_diffrn    1.495
_exptl_crystal_description       Prism
_exptl_crystal_F_000             648
_exptl_crystal_size_max          0.182
_exptl_crystal_size_mid          0.093
_exptl_crystal_size_min          0.052
_refine_diff_density_max         0.271
_refine_diff_density_min         -0.325
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     200
_refine_ls_number_reflns         2804
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0381
_refine_ls_R_factor_gt           0.0358
_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^)+(0.0531P)^2^+0.5038P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0954
_refine_ls_wR_factor_ref         0.0976
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2596
_reflns_number_total             2804
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc06622f2.cif
_cod_data_source_block           exp_1618
_cod_database_code               7129498
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C16 H13 N3 O2 S'
_chemical_oxdiff_usercomment     amrita-722_20210830_Cu
_diffrn_oxdiff_ac3_digest_frames
;
0112d4bcda60f4f4b99426578b1b0fd37b00081e26c
;
_diffrn_oxdiff_ac3_digest_hkl
;
01b6651a2bd0c3d81b098b0780eb9e6b5105b4
;
_reflns_odcompleteness_completeness 99.05
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7), C2(H2), C6(H6)
2.b Aromatic/amide H refined with riding coordinates:
 C15(H15), C18(H18), C12(H12), C11(H11), C17(H17), C16(H16), C13(H13)
2.c Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C)
;
_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 1.997
_oxdiff_exptl_absorpt_empirical_full_min 0.579