Highly Regioselective, Sequential, and Multiple Palladium-Catalyzed Arylations of Vinyl Ethers Carrying a Coordinating Auxiliary: An Example of a Heck Triarylation Process
Peter Nilsson; Mats Larhed; Anders Hallberg; Journal of the American Chemical Society 123 (2001) 8217–8225; doi:10.1021/ja011019k

data_4115666
_publ_contact_author_address
;
 Organic Pharmaceutical Chemistry
 Uppsala University
 Box 574
 SE-751 23 Uppsala
 Sweden
;
_publ_contact_author_email
;
 anders.hallberg@farmkemi.uu.se
;
_publ_contact_author_fax
;
 +46(0)184714474
;
_publ_contact_author_name
;
 Anders Hallberg
;
_publ_contact_author_phone
;
 +46(0)184714284
;
_publ_section_title
;
 Highly Regioselective, Sequential, and Multiple Palladium-Catalyzed
 Arylations of Vinyl Ethers Carrying a Coordinating Auxiliary: An Example
 of a Heck Triarylation Process
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8217
_journal_page_last               8225
_journal_paper_doi               10.1021/ja011019k
_journal_volume                  123
_journal_year                    2001
_chemical_formula_sum            'C36 H42 Cl2 N2 O2 Pd'
_chemical_formula_weight         712.02
_chemical_name_systematic
;
 Dichloro bis-{N,N-Dimethyl-2[(2,2 diphenyl) ethenyloxy]ethanamine}
 palladium(II)

;
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_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     direct
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                90.00
_cell_angle_beta                 99.220(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   17.9444(13)
_cell_length_b                   11.6019(9)
_cell_length_c                   8.2731(6)
_cell_measurement_reflns_used    2199
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      23.133
_cell_measurement_theta_min      2.300
_cell_volume                     1700.1(2)
_computing_cell_refinement       'Bruker AXS Smart software'
_computing_data_collection       'Bruker AXS Smart software'
_computing_data_reduction        'Bruker AXS Smart software'
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 8.1920
_diffrn_measured_fraction_theta_full 0.921
_diffrn_measured_fraction_theta_max 0.921
_diffrn_measurement_device_type  'Bruker AXS Smart APEX'
_diffrn_measurement_method       'CCD, Smart APEX'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0466
_diffrn_reflns_av_sigmaI/netI    0.0818
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            10122
_diffrn_reflns_theta_full        28.09
_diffrn_reflns_theta_max         28.09
_diffrn_reflns_theta_min         2.10
_exptl_absorpt_coefficient_mu    0.736
_exptl_absorpt_correction_T_max  0.96212
_exptl_absorpt_correction_T_min  0.90678
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   'XPREP (Sheldrick, 1997)'
_exptl_crystal_colour            Yellow
_exptl_crystal_density_diffrn    1.391
_exptl_crystal_description       'Rod with square cross section'
_exptl_crystal_F_000             736
_exptl_crystal_preparation
;
Crystal coated with poly-styren to protect from air. N,N-Dimethyl-2-
[(2,2 diphenyl) ethenyloxy]ethanamine (0.13g)was dissolved in 2.5 mL dry
pentane. A Smith process vial containing 0.14g PdCl2(CH3CN)2 in 5 mL dry
acetonitrile was very carefully layered with the enol ether solution under
nitrogen atmosphere and thereafter closed with  a rubber septa. The crystals
were allowed to grow for a few days in the dark, before they were quickly
filtered off and washed with acetonitrile for subsequent X-ray analysis.
The crystals were stored under nitrogen atmosphere.
;
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.783
_refine_diff_density_min         -0.624
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.789
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     280
_refine_ls_number_reflns         3815
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.789
_refine_ls_R_factor_all          0.0837
_refine_ls_R_factor_gt           0.0385
_refine_ls_shift/su_max          0.021
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0156P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0543
_refine_ls_wR_factor_ref         0.0605
_reflns_number_gt                2180
_reflns_number_total             3815
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja011019k_2.cif
_cod_data_source_block           complex14
_cod_database_code               4115666