Pd(0)/Cu(I)-Mediated Direct Arylation of 2'-Deoxyadenosines: Mechanistic Role of Cu(I) and Reactivity Comparisons with Related Purine Nucleosides
Thomas E. Storr; Christoph G. Baumann; Robert J. Thatcher; Sara De Ornellas; Adrian C. Whitwood; Ian J. S. Fairlamb; Journal of Organic Chemistry 74 (2009) 5810–5821; doi:10.1021/jo9012282

data_4024784
_publ_section_title
;
Pd(0)/Cu(I)-Mediated Direct Arylation of 2'-Deoxyadenosines: Mechanistic
Role of Cu(I) and Reactivity Comparisons with Related Purine Nucleosides
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              5810
_journal_page_last               5821
_journal_paper_doi               10.1021/jo9012282
_journal_volume                  74
_journal_year                    2009
_chemical_absolute_configuration syn
_chemical_formula_moiety         '2(C20 H19 N5 O3), C H4 O, H2 O'
_chemical_formula_sum            'C41 H44 N10 O8'
_chemical_formula_weight         804.86
_space_group_IT_number           1
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date
;
'Thu Jul 24 16:10:21 2008'
;
_audit_creation_method
;
CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.32.24 (release 21-04-2008 CrysAlis171 .NET)
(compiled Apr 21 2008,18:23:10)
;
_cell_angle_alpha                93.768(2)
_cell_angle_beta                 94.058(3)
_cell_angle_gamma                101.822(3)
_cell_formula_units_Z            1
_cell_length_a                   7.8036(3)
_cell_length_b                   10.1562(3)
_cell_length_c                   12.3581(3)
_cell_measurement_reflns_used    7646
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      70.3344
_cell_measurement_theta_min      5.4957
_cell_volume                     953.03(5)
_computing_cell_refinement
;
CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.32.24 (release 21-04-2008 CrysAlis171 .NET)
(compiled Apr 21 2008,18:23:10)
;
_computing_data_collection
;
CrysAlis CCD, Oxford Diffraction Ltd.,
Version 1.171.32.24 (release 21-04-2008 CrysAlis171 .NET)
(compiled Apr 21 2008,18:23:10)
;
_computing_data_reduction
;
CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.32.24 (release 21-04-2008 CrysAlis171 .NET)
(compiled Apr 21 2008,18:23:10)
;
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1997)'
_diffrn_ambient_temperature      120(2)
_diffrn_detector_area_resol_mean 8.2707
_diffrn_measured_fraction_theta_full 0.957
_diffrn_measured_fraction_theta_max 0.957
_diffrn_measurement_details
;
  1 omega  -42.00   11.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -13.7937   45.0000  300.0000    0.0000    0.0000 53

  2 omega  -38.00   14.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -13.7937  -45.0000  330.0000    0.0000    0.0000 52

  3 omega  -38.00   15.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -13.7937  -45.0000   60.0000    0.0000    0.0000 53

  4 omega   13.00   73.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -13.7937    0.0000   30.0000    0.0000    0.0000 60

  5 omega  -20.00   38.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -       13.7937   77.0000  300.0000    0.0000    0.0000 58

  6 omega   35.00   87.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -       13.7937   45.0000  330.0000    0.0000    0.0000 52

  7 omega  -53.00  -15.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -       13.7937  -45.0000  120.0000    0.0000    0.0000 38

  8 omega -127.00  -14.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -93.0000   77.0000  270.0000    0.0000    0.0000 113

  9 omega  -72.00  -19.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -93.0000   45.0000  180.0000    0.0000    0.0000 53

 10 omega -178.00   -6.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -93.0000    0.0000  300.0000    0.0000    0.0000 172

 11 omega -126.00  -68.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -93.0000   77.0000    0.0000    0.0000    0.0000 58

 12 omega -127.00  -17.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -93.0000   77.0000   90.0000    0.0000    0.0000 110

 13 omega   75.00  128.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000  -45.0000   90.0000    0.0000    0.0000 53

 14 omega   76.00  134.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000  -77.0000  270.0000    0.0000    0.0000 58

 15 omega  121.00  167.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000   45.0000  300.0000    0.0000    0.0000 46

 16 omega   26.00   79.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000  -45.0000  330.0000    0.0000    0.0000 53

 17 omega   29.00   79.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000  -45.0000  270.0000    0.0000    0.0000 50

 18 omega   78.00  115.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000 -111.0000   58.0000    0.0000    0.0000 37

 19 omega   86.00  113.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000 -115.0000  252.0000    0.0000    0.0000 27

 20 omega   23.00  108.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000 -118.0000  143.0000    0.0000    0.0000 85

 21 omega   73.00  117.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000   45.0000   90.0000    0.0000    0.0000 44

 22 omega  143.00  170.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000   45.0000   60.0000    0.0000    0.0000 27

 23 omega   72.00  106.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000   77.0000  240.0000    0.0000    0.0000 34

;
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'Phi & Omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'Enhance (Cu) X-ray Source'
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0217
_diffrn_reflns_av_sigmaI/netI    0.0153
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            7241
_diffrn_reflns_theta_full        70.50
_diffrn_reflns_theta_max         70.50
_diffrn_reflns_theta_min         5.50
_exptl_absorpt_coefficient_mu    0.826
_exptl_absorpt_correction_T_max  0.900
_exptl_absorpt_correction_T_min  0.692
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.32.24 (release 21-04-2008 CrysAlis171 .NET)
(compiled Apr 21 2008,18:23:10)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.402
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             424
_exptl_crystal_size_max          0.75
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.271
_refine_diff_density_min         -0.218
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.09(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     577
_refine_ls_number_reflns         4386
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0335
_refine_ls_R_factor_gt           0.0333
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0771P)^2^+0.1321P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0925
_refine_ls_wR_factor_ref         0.0929
_reflns_number_gt                4345
_reflns_number_total             4386
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo9012282_si_002_4.cif
_cod_data_source_block           ijf0830
_cod_database_code               4024784