Lewis base catalyzed regioselective cyclization of allene ketones or α-methyl allene ketones with unsaturated pyrazolones.
Cheng, Cheng; Sun, Xiaobin; Wu, Zelin; Liu, Qianwei; Xiong, Liqiang; Miao, Zhiwei; Organic & biomolecular chemistry 17 (2019) 3232–3238; doi:10.1039/c9ob00179d

data_7156705
_publ_section_title
;
 Lewis base catalyzed regioselective cyclization of allene ketones or
 \a-methyl allene ketones with unsaturated pyrazolones.
;
_journal_issue                   12
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3232
_journal_page_last               3238
_journal_paper_doi               10.1039/c9ob00179d
_journal_volume                  17
_journal_year                    2019
_chemical_formula_moiety         'C28 H24 N2 O2'
_chemical_formula_sum            'C28 H24 N2 O2'
_chemical_formula_weight         420.49
_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     dual
_audit_creation_date             2017-07-03
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2018-06-23 deposited with the CCDC.    2019-02-26 downloaded from the CCDC.
;
_cell_angle_alpha                68.356(2)
_cell_angle_beta                 80.275(2)
_cell_angle_gamma                62.538(2)
_cell_formula_units_Z            4
_cell_length_a                   12.5063(3)
_cell_length_b                   13.3807(2)
_cell_length_c                   16.7023(3)
_cell_measurement_reflns_used    52206
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      79.1730
_cell_measurement_theta_min      2.8490
_cell_volume                     2305.20(9)
_computing_cell_refinement       'CrysAlisPro 1.171.39.3a (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.3a (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.3a (Rigaku OD, 2015)'
_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      293(2)
_diffrn_detector                 PILT
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.956
_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   -114.00 -21.00   1.00    5.00    --  -35.00 -72.00   0.00   93
  2  \w   -115.00 -21.00   1.00    5.00    --  -35.00 -44.00 108.00   94
  3  \w   -114.00 -21.00   1.00    5.00    --  -35.00 -72.00 -36.00   93
  4  \w    -50.00  40.00   1.00    5.00    --  -35.00  72.00-108.00   90
  5  \w   -112.00 -21.00   1.00    5.00    --  -35.00 -72.00 108.00   91
  6  \w    -50.00  40.00   1.00    5.00    --  -35.00  72.00 -72.00   90
  7  \w   -114.00 -21.00   1.00    5.00    --  -35.00 -72.00  72.00   93
  8  \w    -50.00  40.00   1.00    5.00    --  -35.00  72.00 144.00   90
  9  \w   -115.00 -21.00   1.00    5.00    --  -35.00 -44.00-144.00   94
 10  \w    -50.00  40.00   1.00    5.00    --  -35.00  72.00  36.00   90
 11  \w   -115.00 -21.00   1.00    5.00    --  -35.00 -72.00-144.00   94
 12  \w    -50.00  40.00   1.00    5.00    --  -35.00  43.00-180.00   90
 13  \w   -112.00 -21.00   1.00    5.00    --  -35.00 -72.00-108.00   91
 14  \w   -112.00 -21.00   1.00    5.00    --  -35.00 -72.00 144.00   91
 15  \w   -114.00 -21.00   1.00    5.00    --  -35.00 -72.00  36.00   93
 16  \w    -50.00  40.00   1.00    5.00    --  -35.00  72.00 -36.00   90
 17  \w   -115.00 -25.00   1.00    5.00    --  -35.00 -44.00 -36.00   90
 18  \w   -115.00 -25.00   1.00    5.00    --  -35.00 -44.00  72.00   90
 19  \w   -115.00 -25.00   1.00    5.00    --  -35.00 -72.00 -72.00   90
 20  \w   -114.00 -21.00   1.00    5.00    --  -35.00 -72.00-180.00   93
 21  \w    -50.00  40.00   1.00    5.00    --  -35.00  14.00-180.00   90
 22  \w    -35.00  55.00   1.00    5.00    --  -35.00  43.00-144.00   90
 23  \w    -50.00  40.00   1.00    5.00    --  -35.00  14.00  36.00   90
 24  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -44.00-144.00   91
 25  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -44.00   0.00   91
 26  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -44.00 108.00   91
 27  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -44.00-108.00   91
 28  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -44.00 -36.00   91
 29  \w   -125.00 -32.00   1.00    5.00    -- -110.00  72.00 108.00   93
 30  \w   -125.00 -33.00   1.00    5.00    -- -110.00  72.00   0.00   92
 31  \w   -125.00 -33.00   1.00    5.00    -- -110.00  72.00-144.00   92
 32  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -44.00  72.00   91
 33  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -72.00 144.00   91
 34  \w   -187.00 -97.00   1.00    5.00    -- -110.00 -15.00-180.00   90
 35  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -72.00 -36.00   91
 36  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -72.00  36.00   91
 37  \w   -125.00 -31.00   1.00    5.00    -- -110.00  72.00 -36.00   94
 38  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -72.00-108.00   91
 39  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -72.00 -72.00   91
 40  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -72.00   0.00   91
 41  \w   -187.00 -97.00   1.00    5.00    -- -110.00 -15.00  72.00   90
 42  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -72.00-180.00   91
 43  \w   -200.00-110.00   1.00    5.00    -- -110.00 -15.00  36.00   90
 44  \w   -123.00 -33.00   1.00    5.00    -- -110.00  72.00  36.00   90
 45  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -72.00 108.00   91
 46  \w   -125.00 -31.00   1.00    5.00    -- -110.00  72.00-180.00   94
 47  \w   -198.00-105.00   1.00    5.00    -- -110.00 -15.00 144.00   93
 48  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -44.00-180.00   91
 49  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -44.00  36.00   91
 50  \w   -187.00 -97.00   1.00    5.00    -- -110.00 -15.00-108.00   90
 51  \w   -187.00 -97.00   1.00    5.00    -- -110.00 -72.00  72.00   90
 52  \w   -187.00 -97.00   1.00    5.00    -- -110.00 -15.00 108.00   90
 53  \w   -200.00-110.00   1.00    5.00    -- -110.00 -15.00-144.00   90
 54  \w   -200.00-110.00   1.00    5.00    -- -110.00 -15.00 -72.00   90
 55  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -44.00 144.00   91
 56  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -72.00-144.00   91
 57  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -44.00 -72.00   91
 58  \w   -187.00 -97.00   1.00    5.00    -- -110.00 -15.00   0.00   90
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0482759000
_diffrn_orient_matrix_UB_12      -0.0257599000
_diffrn_orient_matrix_UB_13      0.0929332000
_diffrn_orient_matrix_UB_21      -0.0616775000
_diffrn_orient_matrix_UB_22      0.1347166000
_diffrn_orient_matrix_UB_23      -0.0133429000
_diffrn_orient_matrix_UB_31      -0.1146210000
_diffrn_orient_matrix_UB_32      0.0109111000
_diffrn_orient_matrix_UB_33      -0.0321335000
_diffrn_radiation_monochromator  confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0176
_diffrn_reflns_av_unetI/netI     0.0087
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            77402
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.234
_diffrn_reflns_theta_min         2.846
_diffrn_source                   'rotating anode'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.605
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75239
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.3a (Rigaku Oxford Diffraction, 2015)
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    1.212
_exptl_crystal_description       block
_exptl_crystal_F_000             888
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.26
_refine_diff_density_max         0.225
_refine_diff_density_min         -0.264
_refine_diff_density_rms         0.064
_refine_ls_extinction_coef       0.0217(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     613
_refine_ls_number_reflns         9542
_refine_ls_number_restraints     8
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0502
_refine_ls_R_factor_gt           0.0479
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0800P)^2^+0.1960P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1371
_refine_ls_wR_factor_ref         0.1395
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8696
_reflns_number_total             9542
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob00179d2.cif
_cod_data_source_block           p20170629b
_cod_depositor_comments
'Adding full bibliography for 7156702--7156705.cif.'
_cod_database_code               7156705
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C28H24N2O2
_shelx_estimated_absorpt_t_max   0.859
_shelx_estimated_absorpt_t_min   0.821
_reflns_odcompleteness_completeness 95.56
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     78.99
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C14-C15 = C14-C15'
 1.5 with sigma of 0.01
 C14-C16 \\sim C14-C20 \\sim C14-C16' \\sim C14-C20'
 with sigma of 0.01
3. Others
 Sof(H14c)=Sof(H14d)=Sof(C15')=Sof(C16')=Sof(H16')=Sof(C17')=Sof(H17')=
 Sof(C18')=Sof(H18')=Sof(C19')=Sof(H19')=Sof(C20')=Sof(H20')=1-FVAR(1)
 Sof(H14a)=Sof(H14b)=Sof(C15)=Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17)=Sof(C18)=
 Sof(H18)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C6(H6), C6A(H6A)
4.b Secondary CH2 refined with riding coordinates:
 C14(H14a,H14b), C14(H14c,H14d), C14A(H14e,H14f)
4.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C16(H16), C17(H17), C18(H18),
 C19(H19), C20(H20), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28), C9A(H9A),
  C10A(H10A), C11A(H11A), C12A(H12A), C13A(H13A), C16A(H16A), C17A(H17A),
 C18A(H18A), C19A(H19A), C20A(H20A), C24A(H24A), C25A(H25A), C26A(H26A),
 C27A(H27A), C28A(H28A), C16'(H16'), C17'(H17'), C18'(H18'), C19'(H19'),
 C20'(H20')
4.d Fitted hexagon refined as free rotating group:
 C15(C16,C17,C18,C19,C20), C15'(C16',C17',C18',C19',C20')
4.e Idealised Me refined as rotating group:
 C7(H7a,H7b,H7c), C22(H22a,H22b,H22c), C7A(H7Aa,H7Ab,H7Ac), C22A(H22d,H22e,H22f)
;
_shelx_res_checksum              95106
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.350
_oxdiff_exptl_absorpt_empirical_full_min 0.821