# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2006 data_global _journal_coden_Cambridge 182 _publ_contact_author_name 'P. Andrew Evans' _publ_contact_author_address ; Department of Chemistry 800 E. Kirkwood Ave Bloomington, IN 47405-7108 USA ; _publ_contact_author_phone '001 812 855 7368' _publ_contact_author_fax '001 812 855 8300' _publ_contact_author_email paevans@indiana.edu _publ_requested_journal 'Chem. Comm.' _publ_section_title ; Regioselective and enantiospecific rhodium-catalyzed allylic amination with thymine: synthesis of a new conformationally rigid nucleoside ; loop_ _publ_author_name _publ_author_address 'Evans, P. Andrew' ; Department of Chemistry 800 E. Kirkwood Ave Bloomington, IN 47405-7108 USA ; 'Lai, Kwong Wah' ; Department of Chemistry 800 E. Kirkwood Ave Bloomington, IN 47405-7108 USA ; 'Zhang, Hai-Ren' ; Department of Chemistry 800 E. Kirkwood Ave Bloomington, IN 47405-7108 USA ; 'Huffman, John C.' ; Department of Chemistry 800 E. Kirkwood Ave Bloomington, IN 47405-7108 USA ; data_03254 _database_code_depnum_ccdc_archive 'CCDC 284326' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C16 H18 N2 O5' _chemical_formula_weight 318.32 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'P2(1) ' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 6.2583(7) _cell_length_b 7.3007(8) _cell_length_c 16.5882(16) _cell_angle_alpha 90.00 _cell_angle_beta 98.717(3) _cell_angle_gamma 90.00 _cell_volume 749.16(14) _cell_formula_units_Z 2 _cell_measurement_temperature 118(2) _cell_measurement_reflns_used 808 _cell_measurement_theta_min 3.05 _cell_measurement_theta_max 26.41 _exptl_crystal_description cleaved _exptl_crystal_colour colorless _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.30 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.411 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 336 _exptl_absorpt_coefficient_mu 0.106 _exptl_absorpt_correction_type none _exptl_special_details ; ? ; _diffrn_ambient_temperature 118(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_details ' 0.30 degree frames measured for 2.17 seconds each' _diffrn_measurement_method '\w scans' _diffrn_measurement_device 'three-circle goniometer with fixed chi' _diffrn_measurement_device_type 'Bruker Platform goniometer' _diffrn_detector 'CCD area detector' _diffrn_detector_type 'Bruker SMART 6000' _diffrn_detector_area_resol_mean 44.52 _diffrn_standards_decay_% 0.0 _diffrn_reflns_number 4829 _diffrn_reflns_av_R_equivalents 0.0496 _diffrn_reflns_av_sigmaI/netI 0.0553 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -4 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 3.05 _diffrn_reflns_theta_max 27.51 _reflns_number_total 2489 _reflns_number_gt 2212 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker, 1999)' _computing_cell_refinement 'SAINT (Bruker, 1999)' _computing_data_reduction 'SAINT (Bruker, 1999), XTEL (local program)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0409P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.2(11) _refine_ls_number_reflns 2489 _refine_ls_number_parameters 290 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0416 _refine_ls_R_factor_gt 0.0367 _refine_ls_wR_factor_ref 0.0851 _refine_ls_wR_factor_gt 0.0825 _refine_ls_goodness_of_fit_ref 0.985 _refine_ls_restrained_S_all 0.984 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group C1 C 0.1757(4) 0.6410(4) 0.00360(14) 0.0367(6) Uani 1 1 d . . . H1 H 0.685(3) 0.731(4) 0.0684(13) 0.025(6) Uiso 1 1 d . . . C2 C 0.1850(4) 0.6327(5) -0.07953(14) 0.0476(7) Uani 1 1 d . . . C3 C 0.3786(4) 0.6642(4) -0.10757(14) 0.0426(7) Uani 1 1 d . . . C4 C 0.5628(4) 0.7014(4) -0.05384(14) 0.0355(6) Uani 1 1 d . . . C5 C 0.5553(3) 0.7103(3) 0.02921(13) 0.0306(5) Uani 1 1 d . . . C6 C 0.3609(3) 0.6806(3) 0.05785(12) 0.0254(5) Uani 1 1 d . . . C7 C 0.3601(3) 0.6870(3) 0.14753(12) 0.0231(4) Uani 1 1 d . . . O8 O 0.5146(2) 0.7188(3) 0.19793(9) 0.0340(4) Uani 1 1 d . . . O9 O 0.1620(2) 0.6507(2) 0.16627(8) 0.0232(3) Uani 1 1 d . . . C10 C 0.1440(3) 0.6285(3) 0.25120(11) 0.0200(4) Uani 1 1 d . . . C11 C 0.0548(3) 0.7972(3) 0.28839(12) 0.0222(4) Uani 1 1 d . . . C12 C -0.0424(3) 0.7156(3) 0.35983(12) 0.0200(4) Uani 1 1 d . . . C13 C -0.2173(3) 0.8310(3) 0.39001(12) 0.0230(4) Uani 1 1 d . . . C14 C -0.1214(4) 0.9896(3) 0.44350(13) 0.0281(5) Uani 1 1 d . . . C15 C -0.3583(3) 0.7127(3) 0.43563(13) 0.0282(5) Uani 1 1 d . . . O16 O -0.4512(4) 0.7695(3) 0.48983(12) 0.0563(6) Uani 1 1 d . . . N17 N -0.3883(3) 0.5358(3) 0.41008(10) 0.0242(4) Uani 1 1 d . . . C18 C -0.2962(3) 0.4540(3) 0.34710(12) 0.0201(4) Uani 1 1 d . . . O19 O -0.3728(2) 0.3096(2) 0.31656(8) 0.0241(3) Uani 1 1 d . . . N20 N -0.1273(3) 0.5396(2) 0.32537(9) 0.0196(3) Uani 1 1 d . . . C21 C -0.0214(3) 0.4761(3) 0.25732(12) 0.0204(4) Uani 1 1 d . . . C22 C 0.0837(3) 0.2886(3) 0.27386(15) 0.0305(5) Uani 1 1 d . . . O23 O 0.2026(5) 0.2663(4) 0.34325(16) 0.0226(7) Uani 0.530(4) 1 d P . . H24 H 0.033(4) 0.613(4) 0.0226(14) 0.038(7) Uiso 1 1 d . . . H25 H 0.055(4) 0.603(4) -0.1169(15) 0.039(7) Uiso 1 1 d . . . H26 H 0.380(4) 0.655(4) -0.1652(15) 0.039(7) Uiso 1 1 d . . . H27 H 0.701(3) 0.724(3) -0.0714(13) 0.022(5) Uiso 1 1 d . . . H28 H 0.287(3) 0.598(3) 0.2800(12) 0.013(5) Uiso 1 1 d . . . H29 H 0.164(4) 0.898(3) 0.3068(13) 0.026(6) Uiso 1 1 d . . . H30 H -0.061(4) 0.860(3) 0.2491(13) 0.021(5) Uiso 1 1 d . . . H31 H 0.077(4) 0.694(3) 0.4039(13) 0.023(6) Uiso 1 1 d . . . H32 H -0.320(4) 0.871(4) 0.3410(15) 0.030(6) Uiso 1 1 d . . . H33 H -0.242(4) 1.069(4) 0.4586(14) 0.035(7) Uiso 1 1 d . . . H34 H -0.032(4) 0.936(4) 0.4939(17) 0.040(7) Uiso 1 1 d . . . H35 H -0.022(4) 1.070(4) 0.4122(15) 0.038(7) Uiso 1 1 d . . . H36 H -0.472(4) 0.463(4) 0.4358(14) 0.027(6) Uiso 1 1 d . . . H37 H -0.130(3) 0.474(3) 0.2078(11) 0.007(4) Uiso 1 1 d . . . H38 H -0.022(4) 0.200(4) 0.2735(14) 0.029(6) Uiso 1 1 d . . . H40 H 0.309(9) 0.265(8) 0.336(3) 0.042(17) Uiso 0.530(4) 1 d P . . O23A O 0.2284(5) 0.2458(5) 0.22627(19) 0.0281(9) Uani 0.470(4) 1 d P . . H40A H 0.336(8) 0.261(8) 0.248(3) 0.023(14) Uiso 0.470(4) 1 d P . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 C1 0.0276(11) 0.0584(16) 0.0253(11) 0.0002(12) 0.0080(9) 0.0080(11) C2 0.0360(12) 0.085(2) 0.0213(12) -0.0014(14) 0.0017(10) 0.0132(14) C3 0.0461(13) 0.0643(19) 0.0200(11) 0.0084(12) 0.0133(10) 0.0204(14) C4 0.0359(11) 0.0460(14) 0.0286(12) 0.0093(11) 0.0172(9) 0.0089(11) C5 0.0291(10) 0.0378(13) 0.0265(11) 0.0052(10) 0.0086(9) 0.0039(10) C6 0.0282(9) 0.0291(12) 0.0204(10) 0.0042(9) 0.0081(8) 0.0055(9) C7 0.0241(9) 0.0239(10) 0.0225(10) 0.0030(9) 0.0068(8) 0.0014(8) O8 0.0259(7) 0.0533(11) 0.0231(8) 0.0012(8) 0.0053(6) -0.0089(8) O9 0.0222(6) 0.0331(8) 0.0152(7) 0.0027(6) 0.0062(5) 0.0000(6) C10 0.0201(9) 0.0255(10) 0.0149(9) 0.0009(8) 0.0043(7) -0.0014(8) C11 0.0236(9) 0.0237(11) 0.0201(10) 0.0020(9) 0.0061(7) -0.0022(9) C12 0.0215(8) 0.0211(9) 0.0177(9) -0.0007(8) 0.0037(7) -0.0035(8) C13 0.0268(9) 0.0251(10) 0.0180(9) -0.0007(9) 0.0062(8) -0.0018(9) C14 0.0376(11) 0.0251(10) 0.0224(11) -0.0047(10) 0.0074(9) -0.0022(10) C15 0.0328(10) 0.0278(11) 0.0264(11) -0.0017(9) 0.0127(9) -0.0028(9) O16 0.0890(14) 0.0365(11) 0.0582(11) -0.0153(9) 0.0587(11) -0.0147(10) N17 0.0259(8) 0.0281(10) 0.0208(9) 0.0007(8) 0.0103(7) -0.0052(8) C18 0.0192(9) 0.0232(10) 0.0178(10) 0.0016(8) 0.0023(7) -0.0010(8) O19 0.0229(6) 0.0263(8) 0.0237(7) -0.0024(6) 0.0054(5) -0.0047(6) N20 0.0214(7) 0.0206(8) 0.0178(8) -0.0013(7) 0.0057(6) -0.0009(7) C21 0.0217(9) 0.0229(10) 0.0172(9) -0.0017(8) 0.0050(7) -0.0007(8) C22 0.0254(10) 0.0217(11) 0.0469(14) 0.0021(10) 0.0135(9) -0.0004(9) O23 0.0187(14) 0.0290(15) 0.0202(14) 0.0034(12) 0.0036(10) -0.0029(11) O23A 0.0210(17) 0.039(2) 0.0242(17) -0.0110(15) 0.0020(13) 0.0001(15) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag C1 C6 1.386(3) . ? C1 C2 1.390(3) . ? C1 H24 1.01(3) . ? C2 C3 1.382(3) . ? C2 H25 0.97(3) . ? C3 C4 1.373(4) . ? C3 H26 0.96(2) . ? C4 C5 1.387(3) . ? C4 H27 0.97(2) . ? C5 C6 1.389(3) . ? C5 H1 0.97(2) . ? C6 C7 1.489(3) . ? C7 O8 1.201(2) . ? C7 O9 1.349(2) . ? O9 C10 1.440(2) . ? C10 C11 1.521(3) . ? C10 C21 1.533(3) . ? C10 H28 0.97(2) . ? C11 C12 1.532(3) . ? C11 H29 1.02(2) . ? C11 H30 1.01(2) . ? C12 N20 1.473(3) . ? C12 C13 1.525(3) . ? C12 H31 0.97(2) . ? C13 C15 1.516(3) . ? C13 C14 1.525(3) . ? C13 H32 1.00(2) . ? C14 H33 1.02(3) . ? C14 H34 1.01(3) . ? C14 H35 1.05(3) . ? C15 O16 1.215(3) . ? C15 N17 1.363(3) . ? N17 C18 1.401(3) . ? N17 H36 0.90(3) . ? C18 O19 1.235(2) . ? C18 N20 1.324(2) . ? N20 C21 1.468(3) . ? C21 C22 1.525(3) . ? C21 H37 0.984(18) . ? C22 O23 1.283(4) . ? C22 O23A 1.326(4) . ? C22 H38 0.93(3) . ? O23 H40 0.69(6) . ? O23A H40A 0.72(5) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C6 C1 C2 119.8(2) . . ? C6 C1 H24 122.0(13) . . ? C2 C1 H24 118.2(13) . . ? C3 C2 C1 119.8(2) . . ? C3 C2 H25 121.0(14) . . ? C1 C2 H25 119.1(14) . . ? C4 C3 C2 120.5(2) . . ? C4 C3 H26 121.9(15) . . ? C2 C3 H26 117.6(16) . . ? C3 C4 C5 120.2(2) . . ? C3 C4 H27 122.6(13) . . ? C5 C4 H27 117.2(13) . . ? C4 C5 C6 119.7(2) . . ? C4 C5 H1 121.5(13) . . ? C6 C5 H1 118.7(12) . . ? C1 C6 C5 120.02(19) . . ? C1 C6 C7 121.74(18) . . ? C5 C6 C7 118.21(19) . . ? O8 C7 O9 123.26(18) . . ? O8 C7 C6 125.24(18) . . ? O9 C7 C6 111.50(16) . . ? C7 O9 C10 117.30(14) . . ? O9 C10 C11 113.18(17) . . ? O9 C10 C21 107.49(15) . . ? C11 C10 C21 105.52(15) . . ? O9 C10 H28 107.8(11) . . ? C11 C10 H28 110.7(12) . . ? C21 C10 H28 112.2(13) . . ? C10 C11 C12 102.24(17) . . ? C10 C11 H29 115.7(13) . . ? C12 C11 H29 112.1(12) . . ? C10 C11 H30 112.2(13) . . ? C12 C11 H30 110.2(12) . . ? H29 C11 H30 104.6(18) . . ? N20 C12 C13 111.99(16) . . ? N20 C12 C11 101.61(15) . . ? C13 C12 C11 115.36(17) . . ? N20 C12 H31 109.7(14) . . ? C13 C12 H31 110.5(13) . . ? C11 C12 H31 107.2(13) . . ? C15 C13 C12 110.53(18) . . ? C15 C13 C14 110.44(17) . . ? C12 C13 C14 111.82(17) . . ? C15 C13 H32 102.8(14) . . ? C12 C13 H32 107.6(13) . . ? C14 C13 H32 113.3(15) . . ? C13 C14 H33 109.6(14) . . ? C13 C14 H34 107.7(16) . . ? H33 C14 H34 111(2) . . ? C13 C14 H35 110.3(14) . . ? H33 C14 H35 109(2) . . ? H34 C14 H35 109(2) . . ? O16 C15 N17 119.6(2) . . ? O16 C15 C13 123.7(2) . . ? N17 C15 C13 116.56(18) . . ? C15 N17 C18 125.67(18) . . ? C15 N17 H36 118.4(16) . . ? C18 N17 H36 116.0(16) . . ? O19 C18 N20 124.61(18) . . ? O19 C18 N17 119.46(17) . . ? N20 C18 N17 115.92(17) . . ? C18 N20 C21 122.16(17) . . ? C18 N20 C12 124.23(16) . . ? C21 N20 C12 113.28(16) . . ? N20 C21 C22 112.19(17) . . ? N20 C21 C10 102.12(16) . . ? C22 C21 C10 112.68(16) . . ? N20 C21 H37 108.2(10) . . ? C22 C21 H37 111.0(12) . . ? C10 C21 H37 110.2(11) . . ? O23 C22 O23A 98.5(2) . . ? O23 C22 C21 116.8(2) . . ? O23A C22 C21 114.8(2) . . ? O23 C22 H38 103.6(15) . . ? O23A C22 H38 112.6(15) . . ? C21 C22 H38 109.7(15) . . ? C22 O23 H40 107(4) . . ? C22 O23A H40A 109(4) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C6 C1 C2 C3 -0.1(5) . . . . ? C1 C2 C3 C4 0.8(5) . . . . ? C2 C3 C4 C5 -0.9(4) . . . . ? C3 C4 C5 C6 0.3(4) . . . . ? C2 C1 C6 C5 -0.5(4) . . . . ? C2 C1 C6 C7 -178.6(3) . . . . ? C4 C5 C6 C1 0.4(4) . . . . ? C4 C5 C6 C7 178.6(2) . . . . ? C1 C6 C7 O8 179.4(2) . . . . ? C5 C6 C7 O8 1.2(3) . . . . ? C1 C6 C7 O9 -0.1(3) . . . . ? C5 C6 C7 O9 -178.30(19) . . . . ? O8 C7 O9 C10 -7.5(3) . . . . ? C6 C7 O9 C10 172.00(17) . . . . ? C7 O9 C10 C11 101.3(2) . . . . ? C7 O9 C10 C21 -142.55(17) . . . . ? O9 C10 C11 C12 155.36(15) . . . . ? C21 C10 C11 C12 38.09(19) . . . . ? C10 C11 C12 N20 -36.08(18) . . . . ? C10 C11 C12 C13 -157.45(16) . . . . ? N20 C12 C13 C15 42.7(2) . . . . ? C11 C12 C13 C15 158.32(16) . . . . ? N20 C12 C13 C14 166.23(17) . . . . ? C11 C12 C13 C14 -78.2(2) . . . . ? C12 C13 C15 O16 151.5(2) . . . . ? C14 C13 C15 O16 27.2(3) . . . . ? C12 C13 C15 N17 -32.0(3) . . . . ? C14 C13 C15 N17 -156.27(19) . . . . ? O16 C15 N17 C18 178.3(2) . . . . ? C13 C15 N17 C18 1.6(3) . . . . ? C15 N17 C18 O19 -162.9(2) . . . . ? C15 N17 C18 N20 17.9(3) . . . . ? O19 C18 N20 C21 4.4(3) . . . . ? N17 C18 N20 C21 -176.47(17) . . . . ? O19 C18 N20 C12 177.42(18) . . . . ? N17 C18 N20 C12 -3.4(3) . . . . ? C13 C12 N20 C18 -27.2(2) . . . . ? C11 C12 N20 C18 -150.91(17) . . . . ? C13 C12 N20 C21 146.37(17) . . . . ? C11 C12 N20 C21 22.69(19) . . . . ? C18 N20 C21 C22 -64.8(2) . . . . ? C12 N20 C21 C22 121.42(18) . . . . ? C18 N20 C21 C10 174.26(16) . . . . ? C12 N20 C21 C10 0.5(2) . . . . ? O9 C10 C21 N20 -145.16(15) . . . . ? C11 C10 C21 N20 -24.11(19) . . . . ? O9 C10 C21 C22 94.28(19) . . . . ? C11 C10 C21 C22 -144.66(17) . . . . ? N20 C21 C22 O23 -48.1(3) . . . . ? C10 C21 C22 O23 66.5(3) . . . . ? N20 C21 C22 O23A -162.7(2) . . . . ? C10 C21 C22 O23A -48.1(3) . . . . ? _diffrn_measured_fraction_theta_max 0.992 _diffrn_reflns_theta_full 27.51 _diffrn_measured_fraction_theta_full 0.992 _refine_diff_density_max 0.241 _refine_diff_density_min -0.185 _refine_diff_density_rms 0.046