An Unusual Formal Migrative Cycloaddition of Aurone-derived Azadienes: Synthesis of Benzofuran-fused Nitrogen Heterocycles
Feng, Qiang; Wu, An; Zhang, Xinhao; Song, Lijuan; Sun, Jianwei; Chemical Science  (2021) –; doi:10.1039/D1SC00941A

data_1562378
_publ_section_title
;
 An Unusual Formal Migrative Cycloaddition of Aurone-derived Azadienes:
 Synthesis of Benzofuran-fused Nitrogen Heterocycles
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC00941A
_journal_year                    2021
_chemical_formula_moiety         'C37 H47 N O4 S Si'
_chemical_formula_sum            'C37 H47 N O4 S Si'
_chemical_formula_weight         629.90
_chemical_name_systematic
'3-Butyl-2-phenyl-1-tosyl-4-((triisopropylsilyl)oxy)-1,2-dihydrobenzofuro [3,2-b]pyridine'
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-07-31
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2020-11-20 deposited with the CCDC.	2021-04-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.297(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.6691(10)
_cell_length_b                   10.8205(5)
_cell_length_c                   20.3333(13)
_cell_measurement_reflns_used    9181
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.5180
_cell_measurement_theta_min      4.3430
_cell_volume                     3393.3(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3577
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     30.00 113.00   1.00   18.00    --  107.97-111.00-120.00   83
  2  \w    -64.00  29.00   1.00    6.00    --  -40.32  37.00-150.00   93
  3  \w   -122.00   6.00   1.00    6.00    --  -40.32 -19.00  30.00  128
  4  \w      1.00  66.00   1.00    6.00    --   40.32 -99.00  30.00   65
  5  \w     23.00  98.00   1.00    6.00    --   40.32-125.00 -60.00   75
  6  \w     80.00 178.00   1.00   18.00    --  107.97  45.00-180.00   98
  7  \w     25.00 169.00   1.00   18.00    --  107.97 -15.00  30.00  144
  8  \w     79.00 161.00   1.00   18.00    --  107.97  61.00-150.00   82
  9  \w    103.00 136.00   1.00   18.00    --  107.97 111.00 120.00   33
 10  \w    153.00 178.00   1.00   18.00    --  107.97 111.00 120.00   25
 11  \w     74.00 178.00   1.00   18.00    --  107.97  77.00  30.00  104
 12  \w     29.00 142.00   1.00   18.00    --  107.97 -77.00  60.00  113
;
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0274187000
_diffrn_orient_matrix_UB_12      0.1300407000
_diffrn_orient_matrix_UB_13      0.0312237000
_diffrn_orient_matrix_UB_21      0.0789366000
_diffrn_orient_matrix_UB_22      -0.0044302000
_diffrn_orient_matrix_UB_23      -0.0217235000
_diffrn_orient_matrix_UB_31      -0.0546938000
_diffrn_orient_matrix_UB_32      0.0578122000
_diffrn_orient_matrix_UB_33      -0.0725604000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0647
_diffrn_reflns_av_unetI/netI     0.0517
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            18730
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        66.500
_diffrn_reflns_theta_max         67.491
_diffrn_reflns_theta_min         4.342
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           0.80
_diffrn_source_power             0.040
_diffrn_source_target            Cu
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.495
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91900
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.233
_exptl_crystal_description       plate
_exptl_crystal_F_000             1352
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: dichloromethane, hexane'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.366
_refine_diff_density_min         -0.551
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.002
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     565
_refine_ls_number_reflns         6094
_refine_ls_number_restraints     179
_refine_ls_restrained_S_all      1.005
_refine_ls_R_factor_all          0.0726
_refine_ls_R_factor_gt           0.0624
_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^)+(0.0780P)^2^+4.9360P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1655
_refine_ls_wR_factor_ref         0.1728
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4992
_reflns_number_total             6094
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc00941a2.cif
_cod_data_source_block           an13cult
_cod_database_code               1562378
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.807
_reflns_odcompleteness_completeness 99.75
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.46
_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
 O4-C3 \\sim O4A-C3A
 with sigma of 0.02
 Si1-O4 \\sim Si1A-O4A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C47) \\sim Ueq, Uanis(C46A) \\sim Ueq: with sigma of 0.004 and sigma for
terminal atoms of 0.002
Uanis(C49A) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.002
Uanis(C41A) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.002
4. Rigid body (RIGU) restrains
 Si1A, O4A, C2A, C3A, C37A, C38A, C39A, C40A, C42A, C43A, C44A, C45A, C46A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.001
 Si1, O4, C1, C2, C3, C37, C38, C39, C40, C41, C42, C43, C44, C45, C46
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.001
5. Others
 Fixed Sof: Si1(0.6) Si1A(0.4) O4(0.6) O4A(0.4) H1A(0.6) H1B(0.4) C2(0.6)
 C2A(0.4) C3(0.6) C3A(0.4) C37(0.66667) H37A(0.66667) H37B(0.66667)
 C37A(0.33333) H37C(0.33333) H37D(0.33333) C38(0.66667) H38A(0.66667)
 H38B(0.66667) C38A(0.33333) H38C(0.33333) H38D(0.33333) C39(0.66667)
 H39A(0.66667) H39B(0.66667) C39A(0.33333) H39C(0.33333) H39D(0.33333)
 C40(0.66667) H40A(0.66667) H40B(0.66667) H40C(0.66667) C40A(0.33333)
 H40D(0.33333) H40E(0.33333) H40F(0.33333) C41(0.5) H41(0.5) C41A(0.5)
 H41A(0.5) C42(0.5) H42A(0.5) H42B(0.5) H42C(0.5) C42A(0.5) H42D(0.5) H42E(0.5)
 H42F(0.5) C43(0.5) H43A(0.5) H43B(0.5) H43C(0.5) C43A(0.5) H43D(0.5) H43E(0.5)
 H43F(0.5) C44(0.6) H44(0.6) C44A(0.4) H44A(0.4) C45(0.6) H45A(0.6) H45B(0.6)
 H45C(0.6) C45A(0.4) H45D(0.4) H45E(0.4) H45F(0.4) C46(0.6) H46A(0.6) H46B(0.6)
 H46C(0.6) C46A(0.4) H46D(0.4) H46E(0.4) H46F(0.4) C47(0.6) H47(0.6) C47A(0.4)
 H47A(0.4) C48(0.6) H48A(0.6) H48B(0.6) H48C(0.6) C48A(0.4) H48D(0.4) H48E(0.4)
 H48F(0.4) C49(0.6) H49A(0.6) H49B(0.6) H49C(0.6) C49A(0.4) H49D(0.4) H49E(0.4)
 H49F(0.4)
6.a Ternary CH refined with riding coordinates:
 C1(H1A), C1(H1B), C41(H41), C41A(H41A), C44(H44), C44A(H44A), C47(H47),
 C47A(H47A)
6.b Secondary CH2 refined with riding coordinates:
 C37(H37A,H37B), C37A(H37C,H37D), C38(H38A,H38B), C38A(H38C,H38D), C39(H39A,
 H39B), C39A(H39C,H39D)
6.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C22(H22), C23(H23), C25(H25), C26(H26),
 C32(H32), C33(H33), C34(H34), C35(H35), C36(H36)
6.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C40(H40A,H40B,H40C), C40A(H40D,H40E,H40F), C42(H42A,H42B,
 H42C), C42A(H42D,H42E,H42F), C43(H43A,H43B,H43C), C43A(H43D,H43E,H43F),
 C45(H45A,H45B,H45C), C45A(H45D,H45E,H45F), C46(H46A,H46B,H46C), C46A(H46D,H46E,
 H46F), C48(H48A,H48B,H48C), C48A(H48D,H48E,H48F), C49(H49A,H49B,H49C),
 C49A(H49D,H49E,H49F)
;
_shelx_res_checksum              8544
_shelx_hkl_checksum              43212
_olex2_date_sample_data_collection 2018-07-26
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.817
_oxdiff_exptl_absorpt_empirical_full_min 0.798