General and Modular Synthesis of Isomeric 5-Substituted Pyridin-2-yl and 6-Substituted Pyridin-3-yl C-Ribonucleosides Bearing Diverse Alkyl, Aryl, Hetaryl, Amino, Carbamoyl, and Hydroxy Groups
Martin Štefko; Lenka Slavětínská; Blanka Klepetářová; Michal Hocek; Journal of Organic Chemistry 76 (2011) 6619–6635; doi:10.1021/jo200949c

data_4026513
_publ_contact_author_address
;Institute of Organic Chemistry and Biochemistry
Academy of Sciences of the Czech Republic
Flemingovo nam. 2
16010 Prague 6
Czech Republic
;
_publ_contact_author_email       hocek@uochb.cas.cz
_publ_contact_author_fax         '+420 220183559'
_publ_contact_author_name        'Michal Hocek'
_publ_contact_author_phone       '+420 220183324'
_publ_section_title
;
 General and Modular Synthesis of Isomeric 5-Substituted Pyridin-2-yl and
 6-Substituted Pyridin-3-yl C-Ribonucleosides Bearing Diverse Alkyl, Aryl,
 Hetaryl, Amino, Carbamoyl, and Hydroxy Groups
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              6619
_journal_page_last               6635
_journal_paper_doi               10.1021/jo200949c
_journal_volume                  76
_journal_year                    2011
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C28 H54 Br1 N1 O5 Si3'
_chemical_formula_sum            'C28 H54 Br N O5 Si3'
_chemical_formula_weight         648.90
_chemical_name_systematic
;
1\b-(6-Bromopyridin-3-yl)-1,3,5-tri -O-(tert-butyldimethylsilyl)-D-ribofuranose
;
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      19
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.32986(10)
_cell_length_b                   11.95103(15)
_cell_length_c                   35.3621(5)
_cell_measurement_reflns_used    11858
_cell_measurement_temperature    150
_cell_measurement_theta_max      77
_cell_measurement_theta_min      4
_cell_volume                     3520.31(8)
_computing_cell_refinement       'CrysAlis RED, (Oxford Diffraction, 2002)'
_computing_data_collection       'Xcalibur, (Oxford Diffraction, 2002)'
_computing_data_reduction        'CrysAlis RED, (Oxford Diffraction, 2002)'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'SIR92 (Altomare et al., 1994)'
_diffrn_ambient_temperature      150
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Oxford Diffraction XCALIBUR'
_diffrn_measurement_method       '\f & \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.037
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            17910
_diffrn_reflns_theta_full        75.919
_diffrn_reflns_theta_max         77.468
_diffrn_reflns_theta_min         4.466
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.836
_exptl_absorpt_correction_T_max  0.80
_exptl_absorpt_correction_T_min  0.40
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
; 
 Analytical Absorption (De Meulenaer & Tompa, 1965) 
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.224
_exptl_crystal_description       plate
_exptl_crystal_F_000             1384
_exptl_crystal_size_max          0.750
_exptl_crystal_size_mid          0.320
_exptl_crystal_size_min          0.080
_refine_diff_density_max         0.32
_refine_diff_density_min         -0.46
_refine_ls_abs_structure_details 'Flack (1983), 0 Friedel-pairs'
_refine_ls_abs_structure_Flack   0.048(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.9277
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     344
_refine_ls_number_reflns         6927
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0412
_refine_ls_R_factor_gt           0.0380
_refine_ls_shift/su_max          0.0019978
_refine_ls_shift/su_mean         0.0003398
_refine_ls_structure_factor_coef F
_refine_ls_weighting_details
;
 Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) 
 [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] 
 where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax 
 Method = Robust Weighting (Prince, 1982) 
 W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ 
 A~i~ are: 
 18.2 -5.54 15.2 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.0496
_refine_ls_wR_factor_gt          0.0464
_refine_ls_wR_factor_ref         0.0464
_reflns_limit_h_max              10
_reflns_limit_h_min              -10
_reflns_limit_k_max              15
_reflns_limit_k_min              0
_reflns_limit_l_max              44
_reflns_limit_l_min              0
_reflns_number_gt                6927
_reflns_number_total             7383
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   2.89
_oxford_diffrn_Wilson_scale      0.06
_oxford_refine_ls_r_factor_ref   0.0380
_oxford_refine_ls_scale          4.187(6)
_oxford_reflns_number_all        7383
_oxford_reflns_threshold_expression_ref I>2.0\s(I)
_cod_data_source_file            jo200949c_si_001.cif
_cod_data_source_block           1
_cod_original_formula_sum        'C28 H54 Br1 N1 O5 Si3'
_cod_database_code               4026513