The Reactivity of Thymine and Thymidine 5,6-Epoxides with Organometallic Reagents - A Route to Thymidine (6-4) Photoproduct Analogues.
Wrigstedt, Pauli; Kavakka, Jari; Heikkinen, Sami; Nieger, Martin; Räisänen, Minna; Repo, Timo; The Journal of organic chemistry 81 (2016) 3848–3859; doi:10.1021/acs.joc.6b00495

data_4036780
_publ_section_title
;
 The Reactivity of Thymine and Thymidine 5,6-Epoxides with Organometallic
 Reagents - A Route to Thymidine (6-4) Photoproduct Analogues.
;
_journal_issue                   9
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              3848
_journal_page_last               3859
_journal_paper_doi               10.1021/acs.joc.6b00495
_journal_volume                  81
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C29 H50 N2 O6 Si2'
_chemical_formula_sum            'C29 H50 N2 O6 Si2'
_chemical_formula_weight         578.89
_chemical_name_systematic
;
 (5R,6S)-1-((2R,4S,5S)-4-((tert.-butyldimethylsilyl)oxy)methyl)-
tetrahydrofuran-2-yl)-5-hydroxy-3,5-dimethyl-6-phenyldihydro-
pyrimidine-2,4(1H,3H)-dione
;
_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'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2013
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.21605(5)
_cell_length_b                   15.48832(9)
_cell_length_c                   26.12024(14)
_cell_measurement_reflns_used    14633
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      76.56
_cell_measurement_theta_min      5.63
_cell_volume                     3323.87(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_molecular_graphics    SHELXTL-Plus
_computing_publication_material  publCIF
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_solution    SHELXS-97
_diffrn_ambient_temperature      120(2)
_diffrn_detector_area_resol_mean 5.1977
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       'rotation in \w, 1\%'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0212
_diffrn_reflns_av_unetI/netI     0.0273
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            17714
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         76.936
_diffrn_reflns_theta_min         3.317
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.294
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86134
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.157
_exptl_crystal_description       blocks
_exptl_crystal_F_000             1256
_exptl_crystal_size_max          0.300
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.150
_refine_diff_density_max         0.222
_refine_diff_density_min         -0.170
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 2964 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.002(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     357
_refine_ls_number_reflns         6955
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0271
_refine_ls_R_factor_gt           0.0267
_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^)+(0.0359P)^2^+0.4843P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0683
_refine_ls_wR_factor_ref         0.0686
_reflns_Friedel_coverage         0.765
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.984
_reflns_number_gt                6867
_reflns_number_total             6955
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b00495_si_001.cif
_cod_data_source_block           les112
_cod_database_code               4036780
_shelx_estimated_absorpt_t_min   0.698
_shelx_estimated_absorpt_t_max   0.830