Rhodium(III)-Catalyzed Redox-Neutral 1,1-Cyclization of N-Methoxy Benzamides with Maleimides via C-H/N-H/N-O Activation: Detailed Mechanistic Investigation.
Ramesh, Balu; Tamizmani, Masilamani; Jeganmohan, Masilamani; The Journal of organic chemistry 84 (2019) 4058–4071; doi:10.1021/acs.joc.9b00051

data_4034223
_publ_section_title
;
 Rhodium(III)-Catalyzed Redox-Neutral 1,1-Cyclization of N-Methoxy
 Benzamides with Maleimides via C-H/N-H/N-O Activation: Detailed
 Mechanistic Investigation.
;
_journal_issue                   7
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              4058
_journal_page_last               4071
_journal_paper_doi               10.1021/acs.joc.9b00051
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C20 H27 N2 O5 Rh S, H2 O'
_chemical_formula_sum            'C20 H29 N2 O6 Rh S'
_chemical_formula_weight         528.43
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_Int_Tables_number      14
_audit_creation_date             2018-10-24
_audit_creation_method
;
Olex2 1.2
(compiled 2017.07.20 svn.r3457 for OlexSys, GUI svn.r5370)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.057(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.4313(3)
_cell_length_b                   16.3170(7)
_cell_length_c                   17.1584(8)
_cell_measurement_reflns_used    9006
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      25.216
_cell_measurement_theta_min      2.419
_cell_volume                     2316.72(17)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 (Bruker, 2004)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT-2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.9965
_diffrn_measured_fraction_theta_max 0.9965
_diffrn_measurement_device_type  'Bruker axs kappa apex2 CCD Diffractometer'
_diffrn_measurement_method       '\w and \f scan'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0725
_diffrn_reflns_av_unetI/netI     0.0525
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            42975
_diffrn_reflns_theta_full        27.7488
_diffrn_reflns_theta_max         27.75
_diffrn_reflns_theta_min         2.42
_exptl_absorpt_coefficient_mu    0.864
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6701
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0705 before and 0.0574 after correction.
The Ratio of minimum to maximum transmission is 0.8987.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.5149
_exptl_crystal_description       block
_exptl_crystal_F_000             1084.5107
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.5632
_refine_diff_density_min         -1.1550
_refine_diff_density_rms         0.1865
_refine_ls_d_res_high            0.7632
_refine_ls_d_res_low             8.4199
_refine_ls_goodness_of_fit_ref   1.1367
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    40
_refine_ls_number_parameters     285
_refine_ls_number_reflns         5436
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.1364
_refine_ls_R_factor_all          0.0780
_refine_ls_R_factor_gt           0.0359
_refine_ls_shift/su_max          0.0007
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0314P)^2^+1.7744P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0706
_refine_ls_wR_factor_ref         0.0942
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              10
_reflns_limit_h_min              -11
_reflns_limit_k_max              21
_reflns_limit_k_min              0
_reflns_limit_l_max              22
_reflns_limit_l_min              0
_reflns_number_gt                3756
_reflns_number_total             5436
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            jo9b00051_si_003.cif
_cod_data_source_block           BR530
_cod_database_code               4034223
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All O(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O6-H6e = O6-H6d
 0.85 with sigma of 0.02
 H6e-H6d
 1.38 with sigma of 0.02
3.a Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C18(H18)
3.b Idealised Me refined as rotating group:
 C6(H6a,H6b,H6c), C7(H7a,H7b,H7c), C8(H8a,H8b,H8c), C9(H9a,H9b,H9c), C10(H10a,
 H10b,H10c), C11(H11a,H11b,H11c), C12(H12a,H12b,H12c), C20(H20a,H20b,H20c)
;
_olex2_submission_special_instructions 'No special instructions were received'