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_7124331
_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         '2(C16 H13 Cl2 N O4)'
_chemical_formula_sum            'C32 H26 Cl4 N2 O8'
_chemical_formula_weight         708.35
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-24
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-05-01 deposited with the CCDC.    2019-10-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.410(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.9918(5)
_cell_length_b                   7.1290(3)
_cell_length_c                   16.6483(6)
_cell_measurement_reflns_used    10260
_cell_measurement_temperature    150
_cell_measurement_theta_max      30.2800
_cell_measurement_theta_min      1.9370
_cell_volume                     1532.30(10)
_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 0.997
_diffrn_measured_fraction_theta_max 0.997
_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   -110.00  70.00   0.50    8.00    --  -20.00   0.00 -36.00  360
  2  \w    -59.00  -3.50   0.50    8.00    --  -20.00  72.00-108.00  111
  3  \w    -43.50 -12.00   0.50    8.00    --  -20.00  72.00-180.00   63
  4  \w    -36.00  -6.00   0.50    8.00    --  -20.00  72.00 -36.00   60
  5  \w   -110.00  70.00   0.50    8.00    --  -20.00   0.00-108.00  360
  6  \w    -66.50   0.50   0.50    8.00    --  -20.00 -72.00-180.00  134
;
_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      0.0442773000
_diffrn_orient_matrix_UB_12      -0.0581738000
_diffrn_orient_matrix_UB_13      0.0078127000
_diffrn_orient_matrix_UB_21      -0.0319157000
_diffrn_orient_matrix_UB_22      -0.0746634000
_diffrn_orient_matrix_UB_23      0.0106580000
_diffrn_orient_matrix_UB_31      -0.0062916000
_diffrn_orient_matrix_UB_32      -0.0306453000
_diffrn_orient_matrix_UB_33      -0.0407845000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0498
_diffrn_reflns_av_unetI/netI     0.0548
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            15985
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         2.462
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.443
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67681
_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    1.535
_exptl_crystal_description       block
_exptl_crystal_F_000             728
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.244
_refine_diff_density_min         -0.263
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Flack x determined using 1807 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.05(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     417
_refine_ls_number_reflns         5278
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0484
_refine_ls_R_factor_gt           0.0409
_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^)+(0.0311P)^2^+0.6019P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0804
_refine_ls_wR_factor_ref         0.0858
_reflns_Friedel_coverage         0.801
_reflns_Friedel_fraction_full    0.954
_reflns_Friedel_fraction_max     0.954
_reflns_number_gt                4809
_reflns_number_total             5278
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc07164d2.cif
_cod_data_source_block           cmrv-as-287_mo
_cod_original_cell_volume        1532.31(10)
_cod_database_code               7124331
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.957
_shelx_estimated_absorpt_t_min   0.917
_reflns_odcompleteness_completeness 91.72
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     31.11
_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:
 C27(H27), C11(H11), C28(H28), C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C25(H25A,H25B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C18(H18), C21(H21), C5(H5), C2(H2), C22(H22), C31(H31), C30(H30),
 C6(H6), C19(H19), C16(H16), C15(H15)
2.d Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C12(H12A,H12B,H12C)
;
_shelx_res_checksum              5794
_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 1.329
_oxdiff_exptl_absorpt_empirical_full_min 0.752