Palladium-catalyzed Highly Diastereoslective Cascade Dihalogenation of Alkyne-tethered Cylcohexadienones via Umpolung of Palladium Enolate
Volla, Chandra MR; Singh, Anurag; Shukla, Rahul Kumar; Chemical Communications  (2019) –; doi:10.1039/C9CC07164D

data_7124325
_publ_section_title
;
 Palladium-catalyzed Highly Diastereoslective Cascade Dihalogenation of
 Alkyne-tethered Cylcohexadienones via Umpolung of Palladium Enolate
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC07164D
_journal_year                    2019
_chemical_formula_moiety         'C32 H28 O4'
_chemical_formula_sum            'C32 H28 O4'
_chemical_formula_weight         476.54
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-22
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-06-11 deposited with the CCDC.    2019-10-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.621(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.9103(3)
_cell_length_b                   13.8372(5)
_cell_length_c                   20.3954(7)
_cell_measurement_reflns_used    2959
_cell_measurement_temperature    150
_cell_measurement_theta_max      71.4410
_cell_measurement_theta_min      4.3760
_cell_volume                     2486.21(15)
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.981
_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   -191.00 -11.00   1.00    8.00    -- -101.00   0.00 108.00  180
  2  \w   -122.00  58.00   1.00    8.00    --  -32.00   0.00 -36.00  180
  3  \w    -86.00 -11.00   1.00    8.00    -- -101.00  72.00 -36.00   75
  4  \w   -135.00 -24.00   1.00    8.00    -- -101.00  72.00-108.00  111
  5  \w   -191.00-173.00   1.00    8.00    -- -101.00 -72.00-108.00   18
;
_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      0.1357059000
_diffrn_orient_matrix_UB_12      -0.0698614000
_diffrn_orient_matrix_UB_13      0.0125813000
_diffrn_orient_matrix_UB_21      -0.0155130000
_diffrn_orient_matrix_UB_22      -0.0036675000
_diffrn_orient_matrix_UB_23      0.0741661000
_diffrn_orient_matrix_UB_31      -0.1091179000
_diffrn_orient_matrix_UB_32      -0.0866909000
_diffrn_orient_matrix_UB_33      -0.0131772000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0988
_diffrn_reflns_av_unetI/netI     0.1028
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            8742
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        64.981
_diffrn_reflns_theta_max         64.981
_diffrn_reflns_theta_min         3.874
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.661
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66907
_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    1.273
_exptl_crystal_description       plate
_exptl_crystal_F_000             1008
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.031
_refine_diff_density_max         0.345
_refine_diff_density_min         -0.286
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     327
_refine_ls_number_reflns         4151
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0919
_refine_ls_R_factor_gt           0.0622
_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^)+(0.0680P)^2^+0.3986P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1495
_refine_ls_wR_factor_ref         0.1736
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2982
_reflns_number_total             4151
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc07164d2.cif
_cod_data_source_block           cmrv-as-530b_cu
_cod_original_cell_volume        2486.20(15)
_cod_database_code               7124325
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.879
_reflns_odcompleteness_completeness 95.07
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     72.53
_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:
 C28(H28), C27(H27)
2.b Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C23(H23), C4(H4), C11(H11), C19(H19), C20(H20), C5(H5), C1(H1),
 C21(H21), C31(H31), C22(H22), C14(H14), C12(H12), C15(H15), C2(H2), C30(H30)
2.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C32(H32A,H32B,H32C)
;
_shelx_res_checksum              38397
_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 1.664
_oxdiff_exptl_absorpt_empirical_full_min 0.732