Pd-Catalyzed Umpolung of π–Allylpalladium Intermediates: Assembly of All-Carbon α-Vinyl Quaternary Aldehydes through C(sp3)–C(sp3) Coupling
Wang, Huifei; Qiu, Shuxian; Wang, Sasa; Zhai, Hongbin; ACS Catalysis 8 (2018) 11960–; doi:10.1021/acscatal.8b03814

data_4515791
_publ_section_title
;
 Pd-Catalyzed Umpolung of \p--Allylpalladium Intermediates: Assembly of
 All-Carbon \a-Vinyl Quaternary Aldehydes through C(sp3)--C(sp3) Coupling
;
_journal_issue                   12
_journal_name_full               'ACS Catalysis'
_journal_page_first              11960
_journal_paper_doi               10.1021/acscatal.8b03814
_journal_volume                  8
_journal_year                    2018
_chemical_formula_moiety         'C24 H24 N2 O2 S'
_chemical_formula_sum            'C24 H24 N2 O2 S'
_chemical_formula_weight         404.51
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-07-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.603(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.9646(15)
_cell_length_b                   31.521(5)
_cell_length_c                   6.9339(7)
_cell_measurement_reflns_used    1731
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      72.4440
_cell_measurement_theta_min      2.7740
_cell_volume                     2133.4(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (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_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.982
_diffrn_measured_fraction_theta_max 0.955
_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    -45.00 -18.00   1.00    1.00    --  -41.11 -57.00  30.00   27
  2  \w    -62.00  27.00   1.00    1.00    --  -41.11  37.00 120.00   89
  3  \w      1.00  70.00   1.00    1.00    --   41.11 -99.00-120.00   69
  4  \w     36.00  62.00   1.00    2.00    --  106.95 -94.00   0.00   26
  5  \w     83.00 109.00   1.00    2.00    --  106.95 -94.00   0.00   26
  6  \w     37.00 106.00   1.00    2.00    --  106.95 -94.00 150.00   69
  7  \w     34.00 105.00   1.00    2.00    --  106.95-111.00 -30.00   71
  8  \w     85.00 145.00   1.00    2.00    --  106.95 -15.00-150.00   60
  9  \w    106.00 175.00   1.00    2.00    --  106.95 111.00-150.00   69
 10  \w     87.00 174.00   1.00    2.00    --  106.95  45.00  30.00   87
 11  \w     28.00  54.00   1.00    2.00    --  106.95 -15.00-150.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0260452000
_diffrn_orient_matrix_UB_12      -0.0483094000
_diffrn_orient_matrix_UB_13      -0.0200996000
_diffrn_orient_matrix_UB_21      0.0476179000
_diffrn_orient_matrix_UB_22      -0.0062174000
_diffrn_orient_matrix_UB_23      0.1565228000
_diffrn_orient_matrix_UB_31      -0.2201114000
_diffrn_orient_matrix_UB_32      0.0044110000
_diffrn_orient_matrix_UB_33      0.0033116000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0578
_diffrn_reflns_av_unetI/netI     0.0782
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       6
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            7943
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.601
_diffrn_reflns_theta_min         2.804
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.518
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.40413
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (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    1.259
_exptl_crystal_description       block
_exptl_crystal_F_000             856
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.567
_refine_diff_density_min         -0.377
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     263
_refine_ls_number_reflns         4121
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.1276
_refine_ls_R_factor_gt           0.0965
_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^)+(0.1423P)^2^+2.1181P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2589
_refine_ls_wR_factor_ref         0.2933
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2778
_reflns_number_total             4121
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b03814_si_001.cif
_cod_data_source_block           180720
_cod_database_code               4515791
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 98.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B)
2.b Aromatic/amide H refined with riding coordinates:
 N2(H2), C12(H12), C23(H23), C19(H19), C22(H22), C20(H20), C7(H7), C5(H5),
 C16(H16), C9(H9), C14(H14), C10(H10), C4(H4), C3(H3), C2(H2A)
2.c X=CH2 refined with riding coordinates:
 C15(H15A,H15B), C17(H17A,H17B)
2.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C)
;
_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 1.981
_oxdiff_exptl_absorpt_empirical_full_min 0.683