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_7124326
_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         'C18 H16 Br2 O4'
_chemical_formula_sum            'C18 H16 Br2 O4'
_chemical_formula_weight         456.13
_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             2018-07-05
_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                 101.273(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.7764(19)
_cell_length_b                   7.2681(5)
_cell_length_c                   12.7018(11)
_cell_measurement_reflns_used    2079
_cell_measurement_temperature    150
_cell_measurement_theta_max      29.3340
_cell_measurement_theta_min      3.0020
_cell_volume                     1700.0(3)
_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 0.998
_diffrn_measured_fraction_theta_max 0.998
_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   -109.50  16.00   0.50    8.00    --  -20.00   0.00-108.00  251
  2  \w    -69.00  19.00   0.50    8.00    --  -20.00 -72.00-180.00  176
  3  \w    -59.00 -55.50   0.50    8.00    --  -20.00  72.00-180.00    7
;
_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      -0.0065236000
_diffrn_orient_matrix_UB_12      0.0938543000
_diffrn_orient_matrix_UB_13      0.0102116000
_diffrn_orient_matrix_UB_21      0.0378302000
_diffrn_orient_matrix_UB_22      0.0177365000
_diffrn_orient_matrix_UB_23      0.0085280000
_diffrn_orient_matrix_UB_31      -0.0030878000
_diffrn_orient_matrix_UB_32      0.0201461000
_diffrn_orient_matrix_UB_33      -0.0553506000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0632
_diffrn_reflns_av_unetI/netI     0.0971
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            6598
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        24.996
_diffrn_reflns_theta_max         24.996
_diffrn_reflns_theta_min         2.212
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.788
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58010
_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    1.782
_exptl_crystal_description       plate
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.249
_exptl_crystal_size_mid          0.121
_exptl_crystal_size_min          0.021
_refine_diff_density_max         0.858
_refine_diff_density_min         -0.839
_refine_diff_density_rms         0.214
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.130
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     219
_refine_ls_number_reflns         2988
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.130
_refine_ls_R_factor_all          0.0933
_refine_ls_R_factor_gt           0.0575
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0862P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1378
_refine_ls_wR_factor_ref         0.1902
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2148
_reflns_number_total             2988
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc07164d2.cif
_cod_data_source_block           cmrv-as-210b-1_mo
_cod_database_code               7124326
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.906
_shelx_estimated_absorpt_t_min   0.382
_reflns_odcompleteness_completeness 88.61
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     31.04
_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:
 C007(H007), C009(H009)
2.b Secondary CH2 refined with riding coordinates:
 C00K(H00K,H00L)
2.c Aromatic/amide H refined with riding coordinates:
 C00F(H00G), C00G(H00H), C00H(H00I), C00J(H00J), C00M(H00M), C00N(H00N)
2.d Idealised Me refined as rotating group:
 C00D(H00A,H00B,H00C), C00E(H00D,H00E,H00F)
;
_shelx_res_checksum              33707
_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 2.372
_oxdiff_exptl_absorpt_empirical_full_min 0.692