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_4024785
_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         'C16 H16 N6 O5'
_chemical_formula_sum            'C16 H16 N6 O5'
_chemical_formula_weight         372.35
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date
;
'Thu Aug 14 10:01:43 2008'
;
_audit_creation_method
;
SHELXTL v6.1.4.8 (Bruker AXS) 
&
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                90.0
_cell_angle_beta                 103.4584(15)
_cell_angle_gamma                90.0
_cell_formula_units_Z            2
_cell_length_a                   11.53458(17)
_cell_length_b                   4.57235(6)
_cell_length_c                   15.5302(2)
_cell_measurement_reflns_used    5447
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      70.451
_cell_measurement_theta_min      3.9339
_cell_volume                     796.57(2)
_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 0.982
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measurement_details
;
  1 omega  -38.00   15.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -13.7937  -45.0000  150.0000    0.0000    0.0000 53

  2 omega  -60.00   -8.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -       13.7937  -45.0000    0.0000    0.0000    0.0000 52

  3 omega   41.00  101.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -       13.7937    0.0000  300.0000    0.0000    0.0000 60

  4 omega   35.00   88.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -       13.7937   45.0000  150.0000    0.0000    0.0000 53

  5 omega  -20.00   37.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -       13.7937   77.0000    0.0000    0.0000    0.0000 57

  6 omega   30.00   56.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -       13.7937 -158.0000   51.0000    0.0000    0.0000 26

  7 omega  -38.00   14.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -13.7937  -45.0000  330.0000    0.0000    0.0000 52

  8 omega -127.00  -14.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -93.0000   77.0000  330.0000    0.0000    0.0000 113

  9 omega -118.00  -15.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -93.0000  119.0000  154.0000    0.0000    0.0000 103

 10 omega -122.00  -72.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -93.0000   40.0000  265.0000    0.0000    0.0000 50

 11 omega -121.00  -19.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -93.0000   45.0000  150.0000    0.0000    0.0000 102

 12 omega  121.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000    0.0000    0.0000    0.0000    0.0000 57

 13 omega   21.00  133.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000  -77.0000   30.0000    0.0000    0.0000 112

 14 omega   72.00  171.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000   45.0000  150.0000    0.0000    0.0000 99

 15 omega   72.00   98.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000   45.0000   30.0000    0.0000    0.0000 26

 16 omega  141.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000  119.0000  110.0000    0.0000    0.0000 37

 17 omega  121.00  147.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000   45.0000  300.0000    0.0000    0.0000 26

 18 omega   92.00  118.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000 -119.0000  205.0000    0.0000    0.0000 26

 19 omega  110.00  137.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000 -158.0000   95.0000    0.0000    0.0000 27

 20 omega   75.00  125.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000  -45.0000  210.0000    0.0000    0.0000 50

 21 omega   66.00  109.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000   77.0000  180.0000    0.0000    0.0000 43

 22 omega   73.00  103.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000   45.0000  120.0000    0.0000    0.0000 30

 23 omega   89.00  126.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000  -45.0000  150.0000    0.0000    0.0000 37

;
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_orient_matrix_UB_11      -0.0891108796
_diffrn_orient_matrix_UB_12      0.1245769752
_diffrn_orient_matrix_UB_13      0.0505963233
_diffrn_orient_matrix_UB_21      -0.0489914124
_diffrn_orient_matrix_UB_22      -0.3100497801
_diffrn_orient_matrix_UB_23      0.0078201477
_diffrn_orient_matrix_UB_31      0.0921777956
_diffrn_orient_matrix_UB_32      -0.0434044436
_diffrn_orient_matrix_UB_33      0.0883160503
_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  0.0322
_diffrn_reflns_av_sigmaI/netI    0.0195
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            5766
_diffrn_reflns_theta_full        70.46
_diffrn_reflns_theta_max         70.451
_diffrn_reflns_theta_min         3.9339
_exptl_absorpt_coefficient_mu    1.006
_exptl_absorpt_correction_T_max  0.932
_exptl_absorpt_correction_T_min  0.268
_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    1.552
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             388
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.190
_refine_diff_density_min         -0.239
_refine_diff_density_rms         0.057
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.13(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     256
_refine_ls_number_reflns         2907
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0363
_refine_ls_R_factor_gt           0.0347
_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^)+(0.0727P)^2^+0.0872P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0935
_refine_ls_wR_factor_ref         0.0948
_reflns_number_gt                2786
_reflns_number_total             2907
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo9012282_si_002_5.cif
_cod_data_source_block           ijf0838
_cod_original_sg_symbol_H-M      P21
_cod_database_code               4024785