Experimental and Computational Study of the 1,5-O → N Carbamoyl Snieckus-Fries-Type Rearrangement.
Feberero, Claudia; Sedano, Carlos; Suárez-Pantiga, Samuel; López, Carlos Silva; Sanz, Roberto; The Journal of organic chemistry 85 (2020) 12561–12578; doi:10.1021/acs.joc.0c01732

data_4038769
_publ_section_title
;
 Experimental and Computational Study of the 1,5-O \\rightarrow N
 Carbamoyl Snieckus-Fries-Type Rearrangement.
;
_journal_issue                   19
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              12561
_journal_page_last               12578
_journal_paper_doi               10.1021/acs.joc.0c01732
_journal_volume                  85
_journal_year                    2020
_chemical_formula_moiety         'C26 H28 Cl N3 O2'
_chemical_formula_sum            'C26 H28 Cl N3 O2'
_chemical_formula_weight         449.96
_chemical_name_systematic
'o-(E)-4-Chloro-2-(N,N'-di-p-tolylcarbamimidoyl)phenyl N,N-diethylcarbamate ('
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-05-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-05-04 deposited with the CCDC.	2020-06-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.451(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.1225(6)
_cell_length_b                   12.8572(6)
_cell_length_c                   15.2915(8)
_cell_measurement_reflns_used    9964
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.078
_cell_measurement_theta_min      2.310
_cell_volume                     2381.2(2)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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      100(2)
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0493
_diffrn_reflns_av_unetI/netI     0.0285
_diffrn_reflns_Laue_measured_fraction_full 0.994
_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       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            27631
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.104
_diffrn_reflns_theta_max         25.104
_diffrn_reflns_theta_min         2.190
_exptl_absorpt_coefficient_mu    0.188
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8822
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1245 before and 0.0621 after correction. The Ratio of minimum to maximum transmission is 0.8822. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.255
_exptl_crystal_description       needle
_exptl_crystal_F_000             952
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.267
_refine_diff_density_min         -0.304
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     296
_refine_ls_number_reflns         4212
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0448
_refine_ls_R_factor_gt           0.0383
_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^)+(0.0245P)^2^+1.5688P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0829
_refine_ls_wR_factor_ref         0.0875
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3729
_reflns_number_total             4212
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            2001045.cif
_cod_data_source_block           mo_scan_0m_a
_cod_depositor_comments
'Adding full bibliography for 4038765--4038772.cif.'
_cod_database_code               4038769
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.963
_shelx_estimated_absorpt_t_min   0.946
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C00M(H00A,H00B), C00T(H00N,H00Q)
2.b Aromatic/amide H refined with riding coordinates:
 C00C(H00C), C00E(H00E), C00F(H00F), C00G(H00G), C00H(H00H), C00I(H00I),
 C00J(H00J), C00L(H00L), C00O(H00O), C00P(H00P), C00S(H00S)
2.c Idealised Me refined as rotating group:
 C00R(H00D,H00K,H00M), C00U(H00R,H00T,H00U), C00V(H00V,H00W,H00X), C00W(H00Y,H,
 HA)
;
_shelx_res_checksum              21679
_shelx_hkl_checksum              11953
_olex2_submission_special_instructions 'No special instructions were received'