# Supplementary Material (ESI) for Organic & Biomolecular Chemistry
# This journal is (c) The Royal Society of Chemistry 2009



data_global
_journal_name_full               Org.Biomol.Chem.

_journal_coden_Cambridge         0177

_publ_contact_author_name        'Maria Diaz-de-Villegas'
_publ_contact_author_email       LOLADIAZ@UNIZAR.ES

_publ_section_title              
;
Stereocontrolled Synthesis of Orthogonally
Protected 2-Substituted 4-Aminopiperidines
;
loop_
_publ_author_name
'Maria Diaz-de-Villegas'
'Ramon Badorrey'
'Jose A. Galvez'
'Elsa Portana'

# Attachment 'CIF-compound3-new.cif'

data_compound3
_database_code_depnum_ccdc_archive 'CCDC 723555'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_absolute_configuration rm
_chemical_formula_sum            'C30 H37 N O5 S'
_chemical_formula_weight         523.67

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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   'P 21'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y+1/2, -z'

_cell_length_a                   10.0148(6)
_cell_length_b                   10.6959(7)
_cell_length_c                   12.9949(8)
_cell_angle_alpha                90.00
_cell_angle_beta                 102.5750(10)
_cell_angle_gamma                90.00
_cell_volume                     1358.59(15)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    63
_cell_measurement_theta_min      10.2
_cell_measurement_theta_max      12.5

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.44
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.36
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.280
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             560
_exptl_absorpt_coefficient_mu    0.159
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  ?
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            16360
_diffrn_reflns_av_R_equivalents  0.0223
_diffrn_reflns_av_sigmaI/netI    0.0311
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         1.61
_diffrn_reflns_theta_max         28.35
_reflns_number_total             6243
_reflns_number_gt                5994
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_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^)+(0.0602P)^2^+0.3811P] 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    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_abs_structure_details 
'Flack H D (1983), Acta Cryst. A39, 876-881, 2659 Friedel pairs'
_refine_ls_abs_structure_Flack   -0.06(6)
_refine_ls_number_reflns         6243
_refine_ls_number_parameters     334
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0418
_refine_ls_R_factor_gt           0.0401
_refine_ls_wR_factor_ref         0.1028
_refine_ls_wR_factor_gt          0.1018
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_restrained_S_all      1.044
_refine_ls_shift/su_max          0.000
_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
S1 S -0.00149(5) 0.94039(5) 0.50361(3) 0.01761(10) Uani 1 1 d . . .
O1 O 0.09958(13) 0.92385(12) 0.42720(10) 0.0181(3) Uani 1 1 d . . .
O2 O 0.57217(14) 0.58189(13) 0.26469(11) 0.0220(3) Uani 1 1 d . . .
O3 O 0.37189(13) 0.53019(12) 0.41850(10) 0.0191(3) Uani 1 1 d . . .
O4 O -0.04511(16) 0.82022(15) 0.53164(12) 0.0296(3) Uani 1 1 d . . .
O5 O 0.06703(16) 1.02143(15) 0.58523(11) 0.0283(3) Uani 1 1 d . . .
N1 N 0.17487(14) 0.69516(15) 0.18389(11) 0.0145(3) Uani 1 1 d . . .
C1 C 0.3497(2) 0.24956(19) 0.39490(16) 0.0236(4) Uani 1 1 d . . .
H1 H 0.2838 0.2784 0.4297 0.028 Uiso 1 1 calc R . .
C2 C 0.3332(2) 0.1336(2) 0.34433(17) 0.0249(4) Uani 1 1 d . . .
H2 H 0.2566 0.0851 0.3457 0.030 Uiso 1 1 calc R . .
C3 C 0.4311(2) 0.0909(2) 0.29203(16) 0.0253(4) Uani 1 1 d . . .
H3 H 0.4198 0.0138 0.2582 0.030 Uiso 1 1 calc R . .
C4 C 0.5453(2) 0.16240(19) 0.28993(16) 0.0238(4) Uani 1 1 d . . .
H4 H 0.6106 0.1334 0.2546 0.029 Uiso 1 1 calc R . .
C5 C 0.5627(2) 0.27796(19) 0.34064(15) 0.0211(4) Uani 1 1 d . . .
H5 H 0.6399 0.3258 0.3394 0.025 Uiso 1 1 calc R . .
C6 C 0.46494(19) 0.32217(18) 0.39329(14) 0.0183(4) Uani 1 1 d . . .
C7 C 0.5941(2) 0.9307(2) 0.07074(18) 0.0322(5) Uani 1 1 d . . .
H7 H 0.5695 1.0142 0.0748 0.039 Uiso 1 1 calc R . .
C8 C 0.6273(2) 0.8585(2) 0.16127(17) 0.0242(4) Uani 1 1 d . . .
H8 H 0.6257 0.8945 0.2261 0.029 Uiso 1 1 calc R . .
C9 C 0.66312(18) 0.73302(19) 0.15712(16) 0.0206(4) Uani 1 1 d . . .
C10 C 0.6689(2) 0.6821(2) 0.05912(16) 0.0281(4) Uani 1 1 d . . .
H10 H 0.6944 0.5990 0.0547 0.034 Uiso 1 1 calc R . .
C11 C 0.6369(2) 0.7544(3) -0.03176(18) 0.0369(6) Uani 1 1 d . . .
H11 H 0.6419 0.7198 -0.0965 0.044 Uiso 1 1 calc R . .
C12 C 0.5978(2) 0.8772(3) -0.02624(19) 0.0374(6) Uani 1 1 d . . .
H12 H 0.5738 0.9246 -0.0875 0.045 Uiso 1 1 calc R . .
C13 C 0.03794(19) 0.75023(18) 0.16819(14) 0.0187(4) Uani 1 1 d . . .
H13A H -0.0262 0.6876 0.1816 0.022 Uiso 1 1 calc R . .
H13B H 0.0085 0.7775 0.0956 0.022 Uiso 1 1 calc R . .
C14 C 0.0375(2) 0.86116(18) 0.24161(15) 0.0194(4) Uani 1 1 d . . .
H14A H 0.0990 0.9256 0.2270 0.023 Uiso 1 1 calc R . .
H14B H -0.0538 0.8963 0.2308 0.023 Uiso 1 1 calc R . .
C15 C 0.08360(18) 0.81601(17) 0.35422(14) 0.0158(3) Uani 1 1 d . . .
H15 H 0.0165 0.7571 0.3711 0.019 Uiso 1 1 calc R . .
C16 C 0.22253(18) 0.75365(17) 0.36997(14) 0.0161(3) Uani 1 1 d . . .
H16A H 0.2497 0.7227 0.4416 0.019 Uiso 1 1 calc R . .
H16B H 0.2902 0.8141 0.3588 0.019 Uiso 1 1 calc R . .
C17 C 0.21630(18) 0.64461(17) 0.29198(14) 0.0156(3) Uani 1 1 d . . .
H17 H 0.1457 0.5860 0.3033 0.019 Uiso 1 1 calc R . .
C18 C 0.16207(18) 0.66967(16) -0.00657(14) 0.0170(4) Uani 1 1 d . . .
C19 C 0.26153(19) 0.75425(19) -0.02349(15) 0.0206(4) Uani 1 1 d . . .
H19 H 0.3370 0.7705 0.0306 0.025 Uiso 1 1 calc R . .
C20 C 0.2494(2) 0.8143(2) -0.11969(16) 0.0239(4) Uani 1 1 d . . .
H20 H 0.3168 0.8700 -0.1297 0.029 Uiso 1 1 calc R . .
C21 C 0.1367(2) 0.7916(2) -0.20111(16) 0.0259(4) Uani 1 1 d . . .
H21 H 0.1281 0.8322 -0.2655 0.031 Uiso 1 1 calc R . .
C22 C 0.0384(2) 0.7087(2) -0.18551(15) 0.0267(4) Uani 1 1 d . . .
H22 H -0.0369 0.6929 -0.2399 0.032 Uiso 1 1 calc R . .
C23 C 0.0501(2) 0.6480(2) -0.08889(15) 0.0226(4) Uani 1 1 d . . .
H23 H -0.0177 0.5925 -0.0795 0.027 Uiso 1 1 calc R . .
C24 C 0.18397(19) 0.60260(17) 0.09927(14) 0.0169(3) Uani 1 1 d . . .
H24 H 0.2788 0.5729 0.1145 0.020 Uiso 1 1 calc R . .
C25 C 0.0947(2) 0.48655(19) 0.09876(16) 0.0250(4) Uani 1 1 d . . .
H25A H 0.1519 0.4152 0.1207 0.037 Uiso 1 1 calc R . .
H25B H 0.0413 0.4728 0.0288 0.037 Uiso 1 1 calc R . .
H25C H 0.0347 0.4988 0.1464 0.037 Uiso 1 1 calc R . .
C26 C 0.35402(18) 0.57516(17) 0.31250(14) 0.0162(3) Uani 1 1 d . . .
H26 H 0.3464 0.5035 0.2646 0.019 Uiso 1 1 calc R . .
C27 C 0.48459(19) 0.4457(2) 0.45061(14) 0.0202(3) Uani 1 1 d . . .
H27A H 0.4976 0.4304 0.5257 0.024 Uiso 1 1 calc R . .
H27B H 0.5671 0.4850 0.4385 0.024 Uiso 1 1 calc R . .
C28 C 0.47099(18) 0.65852(17) 0.29617(15) 0.0178(4) Uani 1 1 d . . .
H28A H 0.4371 0.7204 0.2422 0.021 Uiso 1 1 calc R . .
H28B H 0.5107 0.7020 0.3611 0.021 Uiso 1 1 calc R . .
C29 C 0.69070(19) 0.6512(2) 0.25353(17) 0.0239(4) Uani 1 1 d . . .
H29A H 0.7639 0.5933 0.2493 0.029 Uiso 1 1 calc R . .
H29B H 0.7211 0.7029 0.3155 0.029 Uiso 1 1 calc R . .
C30 C -0.1405(2) 1.0199(2) 0.42649(16) 0.0264(4) Uani 1 1 d . . .
H30A H -0.1607 0.9855 0.3566 0.040 Uiso 1 1 calc R . .
H30B H -0.1183 1.1069 0.4233 0.040 Uiso 1 1 calc R . .
H30C H -0.2188 1.0110 0.4573 0.040 Uiso 1 1 calc R . .

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
S1 0.0211(2) 0.0181(2) 0.01488(19) -0.00176(17) 0.00668(15) 0.00141(17)
O1 0.0200(6) 0.0162(7) 0.0203(6) -0.0033(5) 0.0088(5) -0.0013(5)
O2 0.0178(6) 0.0190(7) 0.0317(8) 0.0049(6) 0.0110(5) 0.0041(5)
O3 0.0229(7) 0.0192(7) 0.0160(6) 0.0029(5) 0.0061(5) 0.0071(5)
O4 0.0426(9) 0.0228(8) 0.0301(8) -0.0012(6) 0.0224(7) -0.0021(7)
O5 0.0328(8) 0.0328(8) 0.0188(7) -0.0082(6) 0.0048(6) 0.0022(7)
N1 0.0164(6) 0.0151(7) 0.0128(6) -0.0010(6) 0.0046(5) 0.0030(6)
C1 0.0202(9) 0.0245(10) 0.0276(10) 0.0044(8) 0.0085(8) 0.0053(8)
C2 0.0209(10) 0.0217(10) 0.0313(11) 0.0044(8) 0.0044(8) -0.0006(8)
C3 0.0317(11) 0.0193(10) 0.0230(10) 0.0014(8) 0.0017(8) 0.0036(8)
C4 0.0271(10) 0.0229(11) 0.0231(10) 0.0020(8) 0.0089(8) 0.0061(8)
C5 0.0218(9) 0.0218(10) 0.0204(9) 0.0043(7) 0.0059(7) 0.0024(7)
C6 0.0216(9) 0.0171(9) 0.0151(8) 0.0051(7) 0.0018(7) 0.0034(7)
C7 0.0239(10) 0.0281(11) 0.0426(12) 0.0088(10) 0.0033(9) -0.0067(9)
C8 0.0185(9) 0.0249(10) 0.0285(10) -0.0015(8) 0.0038(7) -0.0050(7)
C9 0.0109(8) 0.0266(10) 0.0249(9) -0.0008(8) 0.0050(7) -0.0031(7)
C10 0.0228(9) 0.0322(11) 0.0310(10) -0.0074(9) 0.0092(8) -0.0073(9)
C11 0.0303(11) 0.0585(16) 0.0236(10) -0.0075(10) 0.0094(9) -0.0195(11)
C12 0.0288(11) 0.0492(15) 0.0314(12) 0.0180(11) 0.0006(9) -0.0178(11)
C13 0.0172(8) 0.0223(9) 0.0171(8) -0.0011(7) 0.0047(7) 0.0021(7)
C14 0.0187(9) 0.0198(9) 0.0197(9) 0.0006(7) 0.0044(7) 0.0053(7)
C15 0.0181(8) 0.0128(8) 0.0181(8) -0.0026(7) 0.0073(7) 0.0005(7)
C16 0.0168(8) 0.0167(9) 0.0154(8) 0.0004(7) 0.0048(6) 0.0011(7)
C17 0.0160(8) 0.0157(8) 0.0162(8) 0.0015(7) 0.0061(6) -0.0002(6)
C18 0.0192(8) 0.0149(9) 0.0177(8) -0.0028(6) 0.0060(6) 0.0033(7)
C19 0.0171(9) 0.0261(10) 0.0180(9) 0.0002(7) 0.0022(7) 0.0014(7)
C20 0.0238(10) 0.0246(10) 0.0249(10) 0.0035(8) 0.0084(8) 0.0035(8)
C21 0.0316(10) 0.0302(11) 0.0163(9) 0.0017(8) 0.0062(8) 0.0107(9)
C22 0.0277(10) 0.0324(11) 0.0175(9) -0.0050(8) -0.0010(7) 0.0046(8)
C23 0.0224(9) 0.0242(9) 0.0205(9) -0.0042(7) 0.0036(7) -0.0029(7)
C24 0.0187(9) 0.0164(8) 0.0164(8) -0.0029(7) 0.0060(7) 0.0001(7)
C25 0.0311(11) 0.0185(9) 0.0255(10) -0.0039(8) 0.0066(8) -0.0052(8)
C26 0.0189(9) 0.0153(8) 0.0151(8) 0.0015(6) 0.0050(7) 0.0014(7)
C27 0.0231(9) 0.0202(9) 0.0169(8) 0.0039(8) 0.0037(6) 0.0061(8)
C28 0.0175(8) 0.0169(9) 0.0194(9) 0.0006(7) 0.0050(7) 0.0018(7)
C29 0.0135(8) 0.0265(10) 0.0320(11) 0.0044(8) 0.0054(7) 0.0021(7)
C30 0.0211(9) 0.0355(12) 0.0231(10) -0.0021(9) 0.0058(8) 0.0109(9)

_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
S1 O5 1.4248(15) . ?
S1 O4 1.4300(16) . ?
S1 O1 1.5746(13) . ?
S1 C30 1.749(2) . ?
O1 C15 1.480(2) . ?
O2 C28 1.431(2) . ?
O2 C29 1.434(2) . ?
O3 C26 1.433(2) . ?
O3 C27 1.435(2) . ?
N1 C13 1.465(2) . ?
N1 C17 1.478(2) . ?
N1 C24 1.497(2) . ?
C1 C6 1.395(3) . ?
C1 C2 1.396(3) . ?
C2 C3 1.386(3) . ?
C3 C4 1.381(3) . ?
C4 C5 1.394(3) . ?
C5 C6 1.394(3) . ?
C6 C27 1.508(3) . ?
C7 C8 1.386(3) . ?
C7 C12 1.392(4) . ?
C8 C9 1.393(3) . ?
C9 C10 1.398(3) . ?
C9 C29 1.503(3) . ?
C10 C11 1.389(3) . ?
C11 C12 1.377(4) . ?
C13 C14 1.523(3) . ?
C14 C15 1.514(2) . ?
C15 C16 1.516(2) . ?
C16 C17 1.537(2) . ?
C17 C26 1.538(2) . ?
C18 C23 1.391(3) . ?
C18 C19 1.398(3) . ?
C18 C24 1.524(2) . ?
C19 C20 1.387(3) . ?
C20 C21 1.390(3) . ?
C21 C22 1.373(3) . ?
C22 C23 1.396(3) . ?
C24 C25 1.529(3) . ?
C26 C28 1.523(2) . ?

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
O5 S1 O4 118.78(9) . . ?
O5 S1 O1 105.44(8) . . ?
O4 S1 O1 109.49(8) . . ?
O5 S1 C30 108.96(10) . . ?
O4 S1 C30 109.52(11) . . ?
O1 S1 C30 103.54(8) . . ?
C15 O1 S1 119.81(11) . . ?
C28 O2 C29 112.72(14) . . ?
C26 O3 C27 114.62(13) . . ?
C13 N1 C17 109.88(13) . . ?
C13 N1 C24 111.61(14) . . ?
C17 N1 C24 114.00(14) . . ?
C6 C1 C2 120.03(19) . . ?
C3 C2 C1 120.0(2) . . ?
C4 C3 C2 120.27(19) . . ?
C3 C4 C5 120.06(19) . . ?
C4 C5 C6 120.25(19) . . ?
C5 C6 C1 119.38(18) . . ?
C5 C6 C27 120.63(17) . . ?
C1 C6 C27 119.97(17) . . ?
C8 C7 C12 119.4(2) . . ?
C7 C8 C9 121.4(2) . . ?
C8 C9 C10 118.2(2) . . ?
C8 C9 C29 122.03(19) . . ?
C10 C9 C29 119.7(2) . . ?
C11 C10 C9 120.7(2) . . ?
C12 C11 C10 120.1(2) . . ?
C11 C12 C7 120.2(2) . . ?
N1 C13 C14 110.86(15) . . ?
C15 C14 C13 108.36(15) . . ?
O1 C15 C14 109.78(14) . . ?
O1 C15 C16 106.76(14) . . ?
C14 C15 C16 110.40(15) . . ?
C15 C16 C17 109.90(14) . . ?
N1 C17 C16 108.16(14) . . ?
N1 C17 C26 113.40(14) . . ?
C16 C17 C26 110.24(14) . . ?
C23 C18 C19 118.02(17) . . ?
C23 C18 C24 123.31(17) . . ?
C19 C18 C24 118.63(16) . . ?
C20 C19 C18 121.06(17) . . ?
C19 C20 C21 120.16(19) . . ?
C22 C21 C20 119.35(19) . . ?
C21 C22 C23 120.74(19) . . ?
C18 C23 C22 120.66(19) . . ?
N1 C24 C18 109.37(14) . . ?
N1 C24 C25 114.26(15) . . ?
C18 C24 C25 114.14(16) . . ?
O3 C26 C28 113.05(15) . . ?
O3 C26 C17 104.39(14) . . ?
C28 C26 C17 112.40(15) . . ?
O3 C27 C6 113.47(15) . . ?
O2 C28 C26 108.58(14) . . ?
O2 C29 C9 112.29(15) . . ?

_diffrn_measured_fraction_theta_max 0.941
_diffrn_reflns_theta_full        25
_diffrn_measured_fraction_theta_full 1.000
_refine_diff_density_max         0.464
_refine_diff_density_min         -0.384
_refine_diff_density_rms         0.053