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_7124324
_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 Cl2 O4'
_chemical_formula_sum            'C18 H16 Cl2 O4'
_chemical_formula_weight         367.21
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-23
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2016.08.26 svn.r3337 for Rigaku Oxford Diffraction, GUI svn.r5221)
;
_audit_update_record
;
2019-05-01 deposited with the CCDC.    2019-10-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.0071(5)
_cell_length_b                   8.4037(7)
_cell_length_c                   28.7235(19)
_cell_measurement_reflns_used    4098
_cell_measurement_temperature    150
_cell_measurement_theta_max      30.0550
_cell_measurement_theta_min      2.5300
_cell_volume                     1691.4(2)
_computing_cell_refinement       'CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)'
_computing_data_collection       'CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)'
_computing_data_reduction        'CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)'
_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
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku Saturn724+'
_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   -104.00  19.00   0.50    8.00    --  -20.00 -72.00 -36.00  246
  2  \w    -57.50  53.00   0.50    8.00    --  -20.00  72.00 -36.00  221
  3  \w    -59.00   0.00   0.50    8.00    --  -20.00  72.00-108.00  118
;
_diffrn_measurement_device       'AFC12 (Right): Kappa 3 circle'
_diffrn_measurement_device_type  'Rigaku Saturn724+ (2x2 bin mode)'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0097720000
_diffrn_orient_matrix_UB_12      0.0825073000
_diffrn_orient_matrix_UB_13      0.0046466000
_diffrn_orient_matrix_UB_21      -0.0088807000
_diffrn_orient_matrix_UB_22      0.0165993000
_diffrn_orient_matrix_UB_23      -0.0241214000
_diffrn_orient_matrix_UB_31      -0.1003009000
_diffrn_orient_matrix_UB_32      0.0065604000
_diffrn_orient_matrix_UB_33      0.0026173000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0576
_diffrn_reflns_av_unetI/netI     0.0569
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            9374
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.994
_diffrn_reflns_theta_max         24.994
_diffrn_reflns_theta_min         2.525
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.403
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.38669
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (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    1.442
_exptl_crystal_description       block
_exptl_crystal_F_000             760
_exptl_crystal_size_max          0.187
_exptl_crystal_size_mid          0.118
_exptl_crystal_size_min          0.097
_refine_diff_density_max         0.256
_refine_diff_density_min         -0.320
_refine_diff_density_rms         0.078
_refine_ls_abs_structure_details
;
 Flack x determined using 898 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.40(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.104
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     219
_refine_ls_number_reflns         2971
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.104
_refine_ls_R_factor_all          0.0516
_refine_ls_R_factor_gt           0.0423
_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^)+(0.0570P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0970
_refine_ls_wR_factor_ref         0.1172
_reflns_Friedel_coverage         0.701
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                2610
_reflns_number_total             2971
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc07164d2.cif
_cod_data_source_block           cmrv-as-210a_mo
_cod_database_code               7124324
_reflns_odcompleteness_completeness 93.56
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     31.21
_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:
 C17(H17), C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C8(H8), C5(H5), C7(H7), C15(H15), C14(H14)
2.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C18(H18A,H18B,H18C)
;
_shelx_shelxl_version_number     2014/7
_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 2.088
_oxdiff_exptl_absorpt_empirical_full_min 0.505