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_7157159
_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         'C24 H26 N2 O3'
_chemical_formula_sum            'C24 H26 N2 O3'
_chemical_formula_weight         390.47
_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             2018-10-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                73.252(4)
_cell_angle_beta                 73.789(4)
_cell_angle_gamma                71.074(4)
_cell_formula_units_Z            4
_cell_length_a                   11.7236(5)
_cell_length_b                   11.7540(5)
_cell_length_c                   17.2404(8)
_cell_measurement_reflns_used    7100
_cell_measurement_temperature    294.15
_cell_measurement_theta_max      25.7880
_cell_measurement_theta_min      2.9800
_cell_volume                     2106.24(17)
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      294.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9631
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.972
_diffrn_measured_fraction_theta_max 0.965
_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    -90.00  27.00   1.00   30.00    --  -17.15 -19.00 -30.00  117
  2  \w    -20.00  25.00   1.00   30.00    --  -17.15 -99.00  60.00   45
  3  \w    -20.00  25.00   1.00   30.00    --  -17.15 -99.00-120.00   45
  4  \w    -50.00  39.00   1.00   30.00    --   18.79 -57.00-120.00   89
  5  \w    -90.00  27.00   1.00   30.00    --  -17.15 -19.00 120.00  117
  6  \w    -43.00  25.00   1.00   30.00    --  -17.15  38.00 150.00   68
  7  \w     35.00  95.00   1.00   30.00    --   18.79 178.00 150.00   60
;
_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      0.0585606000
_diffrn_orient_matrix_UB_12      -0.0404415000
_diffrn_orient_matrix_UB_13      0.0051333000
_diffrn_orient_matrix_UB_21      0.0187171000
_diffrn_orient_matrix_UB_22      0.0055980000
_diffrn_orient_matrix_UB_23      -0.0434631000
_diffrn_orient_matrix_UB_31      0.0221509000
_diffrn_orient_matrix_UB_32      0.0510399000
_diffrn_orient_matrix_UB_33      -0.0033950000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0276
_diffrn_reflns_av_unetI/netI     0.0464
_diffrn_reflns_Laue_measured_fraction_full 0.972
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            22533
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         2.478
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.081
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87813
_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    1.231
_exptl_crystal_description       block
_exptl_crystal_F_000             832
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.242
_refine_diff_density_min         -0.310
_refine_diff_density_rms         0.036
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     544
_refine_ls_number_reflns         8322
_refine_ls_number_restraints     54
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0900
_refine_ls_R_factor_gt           0.0580
_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^)+(0.0436P)^2^+0.6839P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1230
_refine_ls_wR_factor_ref         0.1407
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5453
_reflns_number_total             8322
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob01967g4.cif
_cod_data_source_block           ev2028
_cod_depositor_comments
'Adding full bibliography for 7157158--7157159.cif.'
_cod_original_cell_volume        2106.23(18)
_cod_database_code               7157159
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         'C24 H26 N2 O3'
_chemical_oxdiff_usercomment     TN-001R3B
_shelx_estimated_absorpt_t_max   0.996
_shelx_estimated_absorpt_t_min   0.976
_reflns_odcompleteness_completeness 96.52
_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. Restrained distances
 C26-C27 = C26-C27A = C26-C28 = C26-C28A = C26-C29 = C26-C29A
 1.52 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(C27) \\sim Ueq, Uanis(C27A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.01
Uanis(C27) = Uanis(C27A)
Uanis(C28) = Uanis(C28A)
Uanis(C29) = Uanis(C29A)
4. Rigid body (RIGU) restrains
 C26, C27, C27A, C28, C28A, C29, C29A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=Sof(C28A)=Sof(H28D)=Sof(H28E)=
 Sof(H28F)=Sof(C29A)=Sof(H29D)=Sof(H29E)=Sof(H29F)=1-FVAR(1)
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=
 Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C12(H12), C13(H13), C35(H35), C36(H36), C37(H37),
 C41(H41), C42(H42)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C15(H15), C16(H16), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22),
 N25(H25), C32(H32), C44(H44), C45(H45), C47(H47), C48(H48), C49(H49), C50(H50),
  C51(H51), N54(H54)
6.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C27(H27A,H27B,H27C), C27A(H27D,H27E,H27F), C28(H28A,H28B,
 H28C), C28A(H28D,H28E,H28F), C29(H29A,H29B,H29C), C29A(H29D,H29E,H29F),
 C39(H39A,H39B,H39C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C58(H58A,H58B,
 H58C)
;
_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 1.512
_oxdiff_exptl_absorpt_empirical_full_min 0.695