Phosphine-catalyzed dearomative (3 + 2) annulation of 2-nitrobenzofurans and nitrobenzothiophenes with allenoates.
Zhao, Jian-Qiang; Yang, Lei; You, Yong; Wang, Zhen-Hua; Xie, Ke-Xin; Zhang, Xiao-Mei; Xu, Xiao-Ying; Yuan, Wei-Cheng; Organic & biomolecular chemistry 17 (2019) 5294–5304; doi:10.1039/c9ob00775j

data_7156834
_publ_section_title
;
 Phosphine-catalyzed dearomative (3 + 2) annulation of 2-nitrobenzofurans
 and nitrobenzothiophenes with allenoates.
;
_journal_issue                   21
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              5294
_journal_page_last               5304
_journal_paper_doi               10.1039/c9ob00775j
_journal_volume                  17
_journal_year                    2019
_chemical_formula_moiety         'C15 H15 N O6'
_chemical_formula_sum            'C15 H15 N O6'
_chemical_formula_weight         305.28
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-11-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-03-04 deposited with the CCDC.    2019-05-07 downloaded from the CCDC.
;
_cell_angle_alpha                85.888(5)
_cell_angle_beta                 88.194(4)
_cell_angle_gamma                79.004(4)
_cell_formula_units_Z            4
_cell_length_a                   6.9301(3)
_cell_length_b                   12.5301(7)
_cell_length_c                   17.0571(10)
_cell_measurement_reflns_used    4057
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.6090
_cell_measurement_theta_min      4.2850
_cell_volume                     1449.97(13)
_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 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
  1 omega -103.00   -5.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -77.0000 -150.0000 98

  2 omega   -4.00   77.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000 -150.0000 81

  3 omega  -34.00   59.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -37.0000  120.0000 93

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

  5 omega   13.00   87.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734 -118.0000   -5.0000 74

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

  7 omega  -33.00   65.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -77.0000   30.0000 98

  8 omega   15.00   45.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   37.0000    0.0000 30

  9 omega   51.00  105.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   57.0000 -120.0000 54

 10 omega   29.00   62.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   57.0000    0.0000 33

 11 omega  -32.00   34.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -57.0000   60.0000 66

 12 omega   89.00  114.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  120.0000 25

 13 omega   60.00  101.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000    0.0000 41

 14 omega   44.00   92.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000   90.0000 48

 15 omega   64.00   91.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000   30.0000 27

 16 omega   78.00  168.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000 -150.0000 90

 17 omega   39.00  125.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000   30.0000 86

 18 omega  110.00  156.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000   60.0000 46

 19 omega   68.00  124.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  178.0000  -30.0000 56

 20 omega   39.00   78.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000    0.0000 39

 21 omega   38.00   93.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  -90.0000 55

 22 omega   59.00  108.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  -90.0000 49

 23 omega   39.00   90.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000 -150.0000 51

 24 omega   83.00  144.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  -30.0000 61

 25 omega   58.00   84.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  -60.0000 26

 26 omega   60.00  112.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000 -150.0000 52

 27 omega   37.00   87.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -60.0000 50

 28 omega   90.00  137.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000   90.0000 47

 29 omega   38.00   91.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  150.0000 53
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0595870000
_diffrn_orient_matrix_UB_12      0.0809772000
_diffrn_orient_matrix_UB_13      -0.0712844000
_diffrn_orient_matrix_UB_21      0.0369170000
_diffrn_orient_matrix_UB_22      -0.0949336000
_diffrn_orient_matrix_UB_23      -0.0545352000
_diffrn_orient_matrix_UB_31      -0.2153771000
_diffrn_orient_matrix_UB_32      -0.0137178000
_diffrn_orient_matrix_UB_33      0.0121091000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0235
_diffrn_reflns_av_unetI/netI     0.0373
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            10304
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.076
_diffrn_reflns_theta_max         67.076
_diffrn_reflns_theta_min         3.602
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.926
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91901
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.398
_exptl_crystal_description       prism
_exptl_crystal_F_000             640
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.195
_refine_diff_density_min         -0.201
_refine_diff_density_rms         0.040
_refine_ls_extinction_coef       0.0059(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     418
_refine_ls_number_reflns         5176
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0633
_refine_ls_R_factor_gt           0.0496
_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^)+(0.0732P)^2^+0.1934P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1333
_refine_ls_wR_factor_ref         0.1480
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3997
_reflns_number_total             5176
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob00775j2.cif
_cod_data_source_block           201811423
_cod_depositor_comments          'Adding full bibliography for 7156834.cif.'
_cod_original_cell_volume        1449.97(14)
_cod_database_code               7156834
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C15H15O3N2Cl1
_shelx_estimated_absorpt_t_max   0.913
_shelx_estimated_absorpt_t_min   0.837
_reflns_odcompleteness_completeness 99.96
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C13-C14
 1.55 with sigma of 0.02
 C13'-C14'
 1.53 with sigma of 0.02
 C13A-C14A
 1.53 with sigma of 0.02
 C16-C17
 1.55 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C13) = Uanis(C13A)
Uanis(C14) = Uanis(C14A)
Uanis(C13') = Uanis(C16)
Uanis(C14') = Uanis(C17)
4. Others
 Sof(C13A)=Sof(H13C)=Sof(H13D)=Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=1-FVAR(1)
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=FVAR(1)
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=1-FVAR(2)
 Sof(C13')=Sof(H13E)=Sof(H13F)=Sof(C14')=Sof(H14G)=Sof(H14H)=Sof(H14I)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C5(H5), C5'(H5')
5.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C13(H13A,H13B), C13A(H13C,H13D), C2'(H2'A,H2'B), C13'(H13E,H13F),
  C16(H16A,H16B)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C9(H9), C10(H10), C11(H11), C3'(H3'), C9'(H9'), C10'(H10'), C11'(H11')
5.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C14A(H14D,H14E,H14F), C15(H15A,H15B,H15C), C14'(H14G,
 H14H,H14I), C15'(H15D,H15E,H15F), C17(H17A,H17B,H17C)
;
_olex2_submission_special_instructions 'No special instructions were received'