Acylamino-Directed Specific Sequential Difunctionalizations of Anilides via Metal-Free Relay Reactions for p-Oxygen and o-Nitrogen Incorporation.
Wan, Yameng; Zhang, Zhiguo; Ma, Nana; Bi, Jingjing; Zhang, Guisheng; The Journal of organic chemistry 84 (2019) 780–791; doi:10.1021/acs.joc.8b02636

data_4036007
_publ_section_title
;
 Acylamino-Directed Specific Sequential Difunctionalizations of Anilides
 via Metal-Free Relay Reactions for p-Oxygen and o-Nitrogen Incorporation.
;
_journal_issue                   2
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              780
_journal_page_last               791
_journal_paper_doi               10.1021/acs.joc.8b02636
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C10 H9 F3 N2 O4'
_chemical_formula_sum            'C10 H9 F3 N2 O4'
_chemical_formula_weight         278.19
_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     direct
_audit_creation_date             2017-02-28
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_cell_angle_alpha                81.641(9)
_cell_angle_beta                 82.204(10)
_cell_angle_gamma                80.603(10)
_cell_formula_units_Z            2
_cell_length_a                   4.6612(6)
_cell_length_b                   8.2732(9)
_cell_length_c                   15.4139(18)
_cell_measurement_reflns_used    888
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      69.6810
_cell_measurement_theta_min      5.4440
_cell_volume                     576.37(12)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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 0.995
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_details
;
  1 omega  -49.00   37.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000   37.0000 -180.0000 86

  2 omega -108.00  -32.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  178.0000 -120.0000 76

  3 omega -102.00  -15.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -57.0000   30.0000 87

  4 omega    6.00   83.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734 -110.0000  159.0000 77

  5 omega  -32.00   55.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -57.0000  -90.0000 87

  6 omega   57.00  110.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000  -30.0000 53

  7 omega   14.00  107.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   37.0000  -90.0000 93

  8 omega  -34.00   59.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -37.0000  -30.0000 93

  9 omega   -4.00   77.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000   30.0000 81

 10 omega   37.00  115.00   1.0000   11.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000   30.0000 78

 11 omega   38.00  109.00   1.0000   11.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  120.0000 71

 12 omega   37.00   91.00   1.0000   11.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -120.0000 54

 13 omega   57.00  150.00   1.0000   11.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  178.0000  -90.0000 93

 14 omega   38.00   83.00   1.0000   11.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  -30.0000 45

 15 omega   85.00  155.00   1.0000   11.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000   60.0000 70

 16 omega   48.00   77.00   1.0000   11.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  120.0000 29

 17 omega   50.00  119.00   1.0000   11.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000   60.0000 69

 18 omega  110.00  137.00   1.0000   11.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000 -180.0000 27

 19 omega   91.00  122.00   1.0000   11.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000  -30.0000 31

 20 omega   45.00   71.00   1.0000   11.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000  -30.0000 26

 21 omega   46.00  104.00   1.0000   11.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  -90.0000 58

 22 omega   45.00   88.00   1.0000   11.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  150.0000 43

 23 omega   37.00   75.00   1.0000   11.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -150.0000 38

 24 omega   41.00   90.00   1.0000   11.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000 -180.0000 49

 25 omega   63.00  178.00   1.0000   11.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000  150.0000 115
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0502963000
_diffrn_orient_matrix_UB_12      -0.1055520000
_diffrn_orient_matrix_UB_13      0.0890454000
_diffrn_orient_matrix_UB_21      -0.0276743000
_diffrn_orient_matrix_UB_22      0.1582956000
_diffrn_orient_matrix_UB_23      0.0440868000
_diffrn_orient_matrix_UB_31      -0.3323043000
_diffrn_orient_matrix_UB_32      -0.0008815000
_diffrn_orient_matrix_UB_33      0.0216380000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0376
_diffrn_reflns_av_unetI/netI     0.0515
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       3
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            4165
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.821
_diffrn_reflns_theta_min         5.463
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.374
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90656
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.603
_exptl_crystal_description       needle
_exptl_crystal_F_000             284
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.199
_refine_diff_density_min         -0.200
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     183
_refine_ls_number_reflns         2162
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0752
_refine_ls_R_factor_gt           0.0503
_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^)+(0.0731P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1320
_refine_ls_wR_factor_ref         0.1524
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1480
_reflns_number_total             2162
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b02636_si_002.cif
_cod_data_source_block           20170213
_cod_original_cell_volume        576.38(12)
_cod_database_code               4036007
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C54H82N2O1
_reflns_odcompleteness_completeness 99.71
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F1A-F3A
 2.1 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(F2) = Uanis(F2A)
Uanis(F3) = Uanis(F3A)
Uanis(F1) = Uanis(F1A)
4. Others
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C6(H6), N1(H1)
5.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C)
;
_olex2_submission_special_instructions 'No special instructions were received'