Bisphosphine catalyzed sequential [3 + 2] cycloaddition and Michael addition of ynones with benzylidenepyrazolones via dual α',α'-C(sp<sup>3</sup>)-H bifunctionalization to construct cyclopentanone-fused spiro-pyrazolones.
Zhang, Jiayong; Miao, Zhiwei; Organic & biomolecular chemistry 16 (2018) 9461–9471; doi:10.1039/c8ob02675k

data_7156595
_publ_section_title
;
 Bisphosphine catalyzed sequential [3 + 2] cycloaddition and Michael
 addition of ynones with benzylidenepyrazolones via dual
 \a',\a'-C(sp<sup>3</sup>)-H bifunctionalization to construct
 cyclopentanone-fused spiro-pyrazolones.
;
_journal_issue                   48
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              9461
_journal_page_last               9471
_journal_paper_doi               10.1039/c8ob02675k
_journal_volume                  16
_journal_year                    2018
_chemical_formula_moiety         'C31 H24 N2 O2'
_chemical_formula_sum            'C31 H24 N2 O2'
_chemical_formula_weight         456.52
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_symmetry_space_group_name_Hall  '-I 2ya'
_symmetry_space_group_name_H-M   'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-05-18
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2017-08-08 deposited with the CCDC.
2018-11-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.7770(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.50950(10)
_cell_length_b                   15.42510(10)
_cell_length_c                   22.00390(10)
_cell_measurement_reflns_used    28791
_cell_measurement_temperature    294.15
_cell_measurement_theta_max      79.0740
_cell_measurement_theta_min      3.2520
_cell_volume                     4689.56(6)
_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      294.15
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_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   -125.00 -21.00   1.00    5.00    --  -35.00 -72.00-108.00  104
  2  \w   -124.00 -29.00   1.00    5.00    --  -35.00 -72.00-180.00   95
  3  \w    -50.00  40.00   1.00    5.00    --  -35.00  72.00-144.00   90
  4  \w   -125.00 -21.00   1.00    5.00    --  -35.00 -72.00 -72.00  104
  5  \w    -50.00  40.00   1.00    5.00    --  -35.00  72.00-180.00   90
  6  \w   -112.00 -21.00   1.00    5.00    --  -35.00 -15.00  36.00   91
  7  \w   -115.00 -25.00   1.00    5.00    --  -35.00 -44.00 -72.00   90
  8  \w   -115.00 -25.00   1.00    5.00    --  -35.00 -72.00 -36.00   90
  9  \w   -200.00 -96.00   1.00    5.00    -- -110.00 -72.00 -36.00  104
 10  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -72.00-144.00   91
 11  \w   -125.00 -31.00   1.00    5.00    -- -110.00  72.00-108.00   94
 12  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -44.00-108.00   91
 13  \w   -200.00 -96.00   1.00    5.00    -- -110.00 -44.00 -36.00  104
 14  \w   -124.00 -26.00   1.00    5.00    -- -110.00  43.00 -36.00   98
 15  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -44.00-144.00   91
 16  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -44.00 -72.00   91
 17  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -44.00-180.00   91
 18  \w   -125.00 -27.00   1.00    5.00    -- -110.00  72.00  36.00   98
 19  \w   -115.00 -25.00   1.00    5.00    -- -110.00  72.00 -36.00   90
 20  \w   -198.00 -96.00   1.00    5.00    -- -110.00 -72.00 -72.00  102
 21  \w   -125.00 -33.00   1.00    5.00    -- -110.00  14.00   0.00   92
 22  \w   -187.00 -96.00   1.00    5.00    -- -110.00 -72.00-108.00   91
 23  \w   -191.00-101.00   1.00    5.00    -- -110.00 -15.00-180.00   90
 24  \w   -200.00-110.00   1.00    5.00    -- -110.00 -15.00 -72.00   90
 25  \w   -195.00-105.00   1.00    5.00    -- -110.00 -15.00-144.00   90
 26  \w   -125.00 -33.00   1.00    5.00    -- -110.00  72.00 -72.00   92
 27  \w   -187.00 -97.00   1.00    5.00    -- -110.00 -72.00-180.00   90
 28  \w   -187.00 -97.00   1.00    5.00    -- -110.00 -15.00-108.00   90
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  'Rigaku Xtalab P200'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1033241000
_diffrn_orient_matrix_UB_12      -0.0076684000
_diffrn_orient_matrix_UB_13      -0.0049716000
_diffrn_orient_matrix_UB_21      -0.0415848000
_diffrn_orient_matrix_UB_22      -0.0308690000
_diffrn_orient_matrix_UB_23      -0.0696251000
_diffrn_orient_matrix_UB_31      -0.0053012000
_diffrn_orient_matrix_UB_32      0.0946818000
_diffrn_orient_matrix_UB_33      -0.0230772000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0153
_diffrn_reflns_av_unetI/netI     0.0079
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            39753
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.248
_diffrn_reflns_theta_min         3.558
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.641
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83470
_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    1.293
_exptl_crystal_description       block
_exptl_crystal_F_000             1920
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.187
_refine_diff_density_min         -0.136
_refine_diff_density_rms         0.028
_refine_ls_extinction_coef       0.00204(10)
_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   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     318
_refine_ls_number_reflns         5030
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0375
_refine_ls_R_factor_gt           0.0363
_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^)+(0.0520P)^2^+1.4190P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1001
_refine_ls_wR_factor_ref         0.1010
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4756
_reflns_number_total             5030
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8ob02675k2.cif
_cod_data_source_block           p20170518a
_cod_depositor_comments
'Adding full bibliography for 7156594--7156595.cif.'
_cod_database_code               7156595
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C41H32N2O3
_shelx_estimated_absorpt_t_max   0.861
_shelx_estimated_absorpt_t_min   0.841
_reflns_odcompleteness_completeness 98.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     79.00
_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.a Ternary CH refined with riding coordinates:
 C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B)
2.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C15(H15), C19(H19), C11(H11), C16(H16), C12(H12), C18(H18),
 C17(H17), C21(H21), C00R(H00R), C25(H25), C00T(H00T), C22(H22), C00V(H00V),
 C00W(H00W), C00X(H00X), C23(H23), C24(H24)
2.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C)
;
_shelx_res_checksum              8269
_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 1.275
_oxdiff_exptl_absorpt_empirical_full_min 0.838