Tunable Synthesis of Functionalized Cyclohexa-1,3-dienes and 2-Aminobenzophenones/Benzoate from the Cascade Reactions of Allenic Ketones/Allenoate with Amines and Enones.
Feng, Tian; Tian, Miaomiao; Zhang, Xinying; Fan, Xuesen; The Journal of organic chemistry 83 (2018) 5313–5322; doi:10.1021/acs.joc.8b00473

data_4035528
_publ_section_title
;
 Tunable Synthesis of Functionalized Cyclohexa-1,3-dienes and
 2-Aminobenzophenones/Benzoate from the Cascade Reactions of Allenic
 Ketones/Allenoate with Amines and Enones.
;
_journal_issue                   9
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              5313
_journal_page_last               5322
_journal_paper_doi               10.1021/acs.joc.8b00473
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C22 H19 N O'
_chemical_formula_sum            'C22 H19 N O'
_chemical_formula_weight         313.38
_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             2018-02-01
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_cell_angle_alpha                90
_cell_angle_beta                 113.555(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.3662(4)
_cell_length_b                   12.1409(3)
_cell_length_c                   12.5714(4)
_cell_measurement_reflns_used    5945
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.2180
_cell_measurement_theta_min      5.5840
_cell_volume                     1590.25(10)
_computing_cell_refinement       'CrysAlisPro 1.171.39.35c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.35c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.35c (Rigaku OD, 2017)'
_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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0528
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.982
_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   -103.00 -19.00   1.00    1.00    --  -36.07 -57.00-150.00   84
  2  \w    -31.00  53.00   1.00    1.00    --   36.07 -57.00-120.00   84
  3  \w     23.00  89.00   1.00    1.00    --   36.07-125.00-180.00   66
  4  \w    -35.00  65.00   1.00    1.00    --   36.07 -19.00 -30.00  100
  5  \w      1.00  75.00   1.00    1.00    --   36.07 -99.00   0.00   74
  6  \w     19.00 103.00   1.00    1.00    --   36.07  57.00 150.00   84
  7  \w     19.00 103.00   1.00    1.00    --   36.07  57.00   0.00   84
  8  \w     17.00 105.00   1.00    1.00    --   36.07  38.00 150.00   88
  9  \w    -33.00  55.00   1.00    1.00    --   36.07 -38.00  90.00   88
 10  \w     40.00 109.00   1.00    1.00    --  109.31 -95.00  90.00   69
 11  \w     40.00 109.00   1.00    1.00    --  109.31 -95.00-150.00   69
 12  \w     39.00 116.00   1.00    1.00    --  109.31-111.00  90.00   77
 13  \w     91.00 176.00   1.00    1.00    --  109.31  61.00   0.00   85
 14  \w     92.00 178.00   1.00    1.00    --  109.31  45.00  90.00   86
 15  \w     92.00 178.00   1.00    1.00    --  109.31  45.00 -30.00   86
 16  \w     41.00 127.00   1.00    1.00    --  109.31 -45.00-120.00   86
 17  \w    123.00 170.00   1.00    1.00    --  109.31  77.00  30.00   47
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0627712000
_diffrn_orient_matrix_UB_12      -0.0355609000
_diffrn_orient_matrix_UB_13      0.1281526000
_diffrn_orient_matrix_UB_21      -0.1321647000
_diffrn_orient_matrix_UB_22      -0.0369861000
_diffrn_orient_matrix_UB_23      -0.0056781000
_diffrn_orient_matrix_UB_31      0.0225114000
_diffrn_orient_matrix_UB_32      -0.1159292000
_diffrn_orient_matrix_UB_33      -0.0378470000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0209
_diffrn_reflns_av_unetI/netI     0.0232
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            8839
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.455
_diffrn_reflns_theta_min         4.440
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.621
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90608
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.35c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.309
_exptl_crystal_description       block
_exptl_crystal_F_000             664
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.426
_refine_diff_density_min         -0.543
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     218
_refine_ls_number_reflns         3092
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0525
_refine_ls_R_factor_gt           0.0498
_refine_ls_shift/su_max          0.017
_refine_ls_shift/su_mean         0.003
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0886P)^2^+0.6130P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1329
_refine_ls_wR_factor_ref         0.1361
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2877
_reflns_number_total             3092
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b00473_si_002.cif
_cod_data_source_block           9b
_cod_database_code               4035528
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C1 N1 O1 H1 Br1'
_reflns_odcompleteness_completeness 99.93
_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. Rigid bond restraints
 C14
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(C14) \\sim Ueq: with sigma of 0.0001 and sigma for terminal atoms of
0.0002
4.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C9(H9), C10(H10), C12(H12), C18(H18),
 C19(H19), C20(H20), C21(H21), C22(H22)
4.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C)
;
_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 1.573
_oxdiff_exptl_absorpt_empirical_full_min 0.494