[8+2] vs [4+2] Cycloadditions of Cyclohexadienamines to Tropone and Heptafulvenes-Mechanisms and Selectivities.
Chen, Xiangyang; Thøgersen, Mathias Kirk; Yang, Limin; Lauridsen, Rune F.; Xue, Xiao-Song; Jørgensen, Karl Anker; Houk, K. N.; Journal of the American Chemical Society 143 (2021) 934–944; doi:10.1021/jacs.0c10966

data_4135563
_publ_section_title
;
 [8+2] vs [4+2] Cycloadditions of Cyclohexadienamines to Tropone and
 Heptafulvenes-Mechanisms and Selectivities.
;
_journal_issue                   2
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              934
_journal_page_last               944
_journal_paper_doi               10.1021/jacs.0c10966
_journal_volume                  143
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H24 Br N5 O5'
_chemical_formula_sum            'C25 H24 Br N5 O5'
_chemical_formula_weight         554.40
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-05-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.1694(3)
_cell_length_b                   16.0398(4)
_cell_length_c                   17.6507(5)
_cell_measurement_reflns_used    12358
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      32.7160
_cell_measurement_theta_min      3.5420
_cell_volume                     2312.87(12)
_computing_cell_refinement       'CrysAlisPro 1.171.40.78a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.78a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.78a (Rigaku OD, 2020)'
_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_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3590
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.947
_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     -5.00  90.00   1.00   20.00    --   16.52  29.00 136.00   95
  2  \w    -57.00  15.00   1.00   20.00    --  -17.46 101.00-110.00   72
  3  \w    -42.00  13.00   1.00   20.00    --  -17.46 -77.00-150.00   55
  4  \w    -42.00  13.00   1.00   20.00    --  -17.46 -77.00 -30.00   55
  5  \w     39.00 100.00   1.00   20.00    --   16.52 178.00-180.00   61
  6  \w    -55.00 -22.00   1.00   20.00    --   16.52 -38.00 -30.00   33
  7  \w    -38.00  34.00   1.00   20.00    --  -17.46  38.00-180.00   72
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0790674000
_diffrn_orient_matrix_UB_12      0.0157140000
_diffrn_orient_matrix_UB_13      0.0083811000
_diffrn_orient_matrix_UB_21      0.0246153000
_diffrn_orient_matrix_UB_22      -0.0401495000
_diffrn_orient_matrix_UB_23      0.0124295000
_diffrn_orient_matrix_UB_31      0.0259769000
_diffrn_orient_matrix_UB_32      -0.0098640000
_diffrn_orient_matrix_UB_33      -0.0372942000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0539
_diffrn_reflns_av_unetI/netI     0.0435
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.947
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            35397
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.926
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.041
_diffrn_reflns_theta_min         3.398
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.827
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.601
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.78a (Rigaku Oxford Diffraction, 2020)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.592
_exptl_crystal_description       needle
_exptl_crystal_F_000             1136
_exptl_crystal_size_max          0.279
_exptl_crystal_size_mid          0.191
_exptl_crystal_size_min          0.19
_refine_diff_density_max         1.211
_refine_diff_density_min         -0.877
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
;
 Flack x determined using 2680 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.000(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     327
_refine_ls_number_reflns         8108
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0518
_refine_ls_R_factor_gt           0.0405
_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^)+(0.0401P)^2^+1.6591P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0906
_refine_ls_wR_factor_ref         0.0977
_reflns_Friedel_coverage         0.755
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.898
_reflns_number_gt                7027
_reflns_number_total             8108
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c10966_si_002.cif
_cod_data_source_block           mkt002_new
_cod_database_code               4135563
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C26H26BrN5O5
_shelx_estimated_absorpt_t_max   0.723
_shelx_estimated_absorpt_t_min   0.630
_reflns_odcompleteness_completeness 99.72
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_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.a Ternary CH refined with riding coordinates:
 C11(H11), C15(H15), C10(H10)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C8(H8A,H8B), C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 N2(H2), C6(H6), C2(H2A), C20(H20), C3(H3), C18(H18), C19(H19), C16(H16),
 C17(H17)
2.d Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              72899
_shelx_hkl_checksum              71473
_olex2_date_sample_data_collection 2020-05-27
_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 2.008
_oxdiff_exptl_absorpt_empirical_full_min 0.726