Palladium-catalyzed intramolecular oxypalladation-initiated cascade: solvent-dependent chemodivergent approach to functionalized benzazepines and tetrahydroquinolines.
Gupta, Anish; Jandial, Tanvi; Karuppasamy, Muthu; Bhuvanesh, Nattamai; Nagarajan, Subbiah; Maheswari, C. Uma; Sridharan, Vellaisamy; Chemical communications (Cambridge, England) 59 (2023) 5233–5236; doi:10.1039/d3cc01370g

data_7131496
_publ_section_title
;
 Palladium-catalyzed intramolecular oxypalladation-initiated cascade:
 solvent-dependent chemodivergent approach to functionalized benzazepines
 and tetrahydroquinolines.
;
_journal_issue                   35
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              5233
_journal_page_last               5236
_journal_paper_doi               10.1039/d3cc01370g
_journal_volume                  59
_journal_year                    2023
_chemical_formula_moiety         'C32 H25 N O5 S, 0.5(C4 H8 O2)'
_chemical_formula_sum            'C34 H29 N O6 S'
_chemical_formula_weight         579.64
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-06-09
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-07-22 deposited with the CCDC.	2023-03-30 downloaded from the CCDC.
;
_cell_angle_alpha                90.682(2)
_cell_angle_beta                 99.416(2)
_cell_angle_gamma                97.172(2)
_cell_formula_units_Z            2
_cell_length_a                   10.5669(6)
_cell_length_b                   11.3682(6)
_cell_length_c                   11.9934(6)
_cell_measurement_reflns_used    9385
_cell_measurement_temperature    110.00
_cell_measurement_theta_max      29.524
_cell_measurement_theta_min      2.392
_cell_volume                     1409.43(13)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      110.00
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker Quest (PHOTON III)'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0453
_diffrn_reflns_av_unetI/netI     0.0420
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            46933
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.914
_diffrn_reflns_theta_min         1.806
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.164
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.7191
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0855 before and 0.0527 after correction.
The Ratio of minimum to maximum transmission is 0.9639.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.366
_exptl_crystal_description       block
_exptl_crystal_F_000             608
_exptl_crystal_size_max          0.205
_exptl_crystal_size_mid          0.183
_exptl_crystal_size_min          0.102
_refine_diff_density_max         0.476
_refine_diff_density_min         -0.304
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.122
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     409
_refine_ls_number_reflns         8098
_refine_ls_number_restraints     60
_refine_ls_restrained_S_all      1.129
_refine_ls_R_factor_all          0.0642
_refine_ls_R_factor_gt           0.0436
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0758P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1220
_refine_ls_wR_factor_ref         0.1292
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6023
_reflns_number_total             8098
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc01370g2.cif
_cod_data_source_block           ag134
_cod_depositor_comments          'Adding full bibliography for 7131496.cif.'
_cod_database_code               7131496
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.967
_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. Uiso/Uaniso restraints and constraints
O1S \\sim O2S \\sim C1S \\sim C2S \\sim C3S \\sim C4S: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01 within 2A
3. Rigid body (RIGU) restrains
 O1S, O2S, C1S, C2S, C3S, C4S
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Others
 Fixed Sof: O1S(0.5) O2S(0.5) C1S(0.5) H1SA(0.5) H1SB(0.5) H1SC(0.5) C2S(0.5)
 C3S(0.5) H3SA(0.5) H3SB(0.5) C4S(0.5) H4SA(0.5) H4SB(0.5) H4SC(0.5)
5.a Ternary CH refined with riding coordinates:
 C4(H4)
5.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C25(H25A,H25B), C3S(H3SA,H3SB)
5.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16),
 C17(H17), C19(H19), C20(H20), C22(H22), C23(H23), C28(H28), C29(H29), C30(H30),
  C31(H31), C32(H32)
5.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C1S(H1SA,H1SB,H1SC), C4S(H4SA,H4SB,H4SC)
;
_shelx_res_checksum              77241
_shelx_hkl_checksum              4677
_olex2_submission_special_instructions 'No special instructions were received'