A gold-triggered dearomative spirocarbocyclization/Diels-Alder reaction cascade towards diverse bridged N-heterocycles.
He, Yi; Narmon, Thomas; Wu, Danjun; Li, Zhenghua; Van Meervelt, Luc; Van der Eycken, Erik V.; Organic & biomolecular chemistry 17 (2019) 9529–; doi:10.1039/c9ob01967g

data_7157158
_publ_section_title
;
 A gold-triggered dearomative spirocarbocyclization/Diels-Alder reaction
 cascade towards diverse bridged N-heterocycles.
;
_journal_issue                   43
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              9529
_journal_paper_doi               10.1039/c9ob01967g
_journal_volume                  17
_journal_year                    2019
_chemical_formula_moiety         'C25 H28 N2 O3'
_chemical_formula_sum            'C25 H28 N2 O3'
_chemical_formula_weight         404.49
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-23
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.486(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.4238(5)
_cell_length_b                   10.0908(3)
_cell_length_c                   16.9778(7)
_cell_measurement_reflns_used    8698
_cell_measurement_temperature    294
_cell_measurement_theta_max      21.9590
_cell_measurement_theta_min      2.7200
_cell_volume                     2285.04(15)
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      294
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9631
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.996
_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    -20.00  25.00   1.00   30.00    --  -17.15 -99.00 -30.00   45
  2  \w    -20.00  25.00   1.00   30.00    --  -17.15 -99.00-150.00   45
  3  \w    -61.00  56.00   1.00   30.00    --  -17.15  19.00  90.00  117
  4  \w     34.00  95.00   1.00   30.00    --   18.79-178.00-120.00   61
  5  \w     -7.00  91.00   1.00   30.00    --   18.79  38.00 -60.00   98
  6  \w    -20.00  61.00   1.00   30.00    --   18.79 -99.00 -60.00   81
  7  \w    -50.00  39.00   1.00   30.00    --   18.79 -57.00-150.00   89
  8  \w     -3.00  88.00   1.00   30.00    --   18.79  57.00 120.00   91
  9  \w    -86.00 -53.00   1.00   30.00    --  -17.15 -57.00 120.00   33
 10  \w    -20.00  61.00   1.00   30.00    --   18.79 -99.00  90.00   81
 11  \w     -3.00  88.00   1.00   30.00    --   18.79  57.00   0.00   91
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0456493000
_diffrn_orient_matrix_UB_12      0.0007594000
_diffrn_orient_matrix_UB_13      -0.0254713000
_diffrn_orient_matrix_UB_21      -0.0082528000
_diffrn_orient_matrix_UB_22      -0.0673781000
_diffrn_orient_matrix_UB_23      0.0092869000
_diffrn_orient_matrix_UB_31      -0.0259786000
_diffrn_orient_matrix_UB_32      0.0200947000
_diffrn_orient_matrix_UB_33      0.0321296000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0525
_diffrn_reflns_av_unetI/netI     0.0326
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            36041
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.368
_diffrn_reflns_theta_min         2.352
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.077
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73733
_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    1.176
_exptl_crystal_description       block
_exptl_crystal_F_000             864
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.332
_refine_diff_density_min         -0.207
_refine_diff_density_rms         0.038
_refine_ls_extinction_coef       0.0037(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/4 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     277
_refine_ls_number_reflns         4653
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.1043
_refine_ls_R_factor_gt           0.0677
_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^)+(0.0826P)^2^+0.5545P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1724
_refine_ls_wR_factor_ref         0.1975
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2867
_reflns_number_total             4653
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob01967g3.cif
_cod_data_source_block           ev2031
_cod_depositor_comments
'Adding full bibliography for 7157158--7157159.cif.'
_cod_original_cell_volume        2285.05(15)
_cod_database_code               7157158
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         'C25 H28 N2 O3'
_chemical_oxdiff_usercomment     TN-001R48B
_shelx_estimated_absorpt_t_max   0.988
_shelx_estimated_absorpt_t_min   0.981
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C16(H16)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C15(H15), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), N26(H26)
2.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C17(H17A,H17B,H17C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C)
;
_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 1.291
_oxdiff_exptl_absorpt_empirical_full_min 0.740