# Supplementary Material (ESI) for Organic & Biomolecular Chemistry
# This journal is © The Royal Society of Chemistry 2005

data_global

_journal_coden_Cambridge         177

loop_
_publ_author_name
'Steven Ley'
'Alexander J. A. Cobb'
'Johan B. Gold'
'Deborah A. Longbottom'
'David M. Shaw'

_publ_contact_author_name        'Dr Steven Ley'
_publ_contact_author_address     
;
Department of Chemistry
Cambridge University
Lensfield Road
Cambridge
CB3 1EW
UNITED KINGDOM
;

_publ_contact_author_email       SVL1000@CAM.AC.UK

_publ_requested_journal          'Organic & Biomolecular Chemistry'

_publ_section_title              
;
Organocatalysis with Proline Derivatives: Improved
Catalysts for the Asymmetric Mannich, Nitro-Michael and Aldol Reactions
;

data_sl0408
_database_code_depnum_ccdc_archive 'CCDC 256659'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C14 H17 N O3'
_chemical_formula_sum            'C14 H17 N O3'
_chemical_formula_weight         247.29

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           Orthorhombic
_symmetry_space_group_name_H-M   P2(1)2(1)2(1)

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

_cell_length_a                   5.5369(4)
_cell_length_b                   8.5297(8)
_cell_length_c                   27.769(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1311.5(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    180(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       ?
_exptl_crystal_colour            ?
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.07
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.252
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             528
_exptl_absorpt_coefficient_mu    0.088
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.787
_exptl_absorpt_correction_T_max  1.018
_exptl_absorpt_process_details   
;
multi-scan from symmetry-related measurements
Sortav (Blessing 1995)
;

_exptl_special_details           
;
The absolute structure was assigned from the known configuration
of the starting material.  838 Friedel pairs averaged for the
refinement.
;

_diffrn_ambient_temperature      180(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_measurement_device_type  'Nonius Kappa CCD'
_diffrn_measurement_method       'Thin slice ω and φ scans'
_diffrn_reflns_number            4884
_diffrn_reflns_av_R_equivalents  0.0685
_diffrn_reflns_av_sigmaI/netI    0.0586
_diffrn_reflns_limit_h_min       -2
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_theta_min         3.75
_diffrn_reflns_theta_max         27.43
_reflns_number_total             1661
_reflns_number_gt                1289
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Collect (Nonius B.V. 1998)'
_computing_cell_refinement       'HKL Scalepack (Otwinowski & Minor 1997)'
_computing_data_reduction        
;
HKL Denzo and Scalepack (Otwinowski & Minor 1997)
;
_computing_structure_solution    'SIR-92 (Altomare et al. 1994)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick 1997)'
_computing_publication_material  'SHELXL-97 (Sheldrick 1997)'

_refine_special_details          
;
Refinement of F² against ALL reflections.  The weighted R-factor wR and
goodness of fit S are based on F², conventional R-factors R are based
on F, with F set to zero for negative F². The threshold expression of
F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement.  R-factors based
on F² 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/[σ²(Fo²)+(0.0590P)²+0.9507P] where P=(Fo²+2Fc²)/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(4)
_refine_ls_number_reflns         1661
_refine_ls_number_parameters     163
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0855
_refine_ls_R_factor_gt           0.0649
_refine_ls_wR_factor_ref         0.1726
_refine_ls_wR_factor_gt          0.1626
_refine_ls_goodness_of_fit_ref   1.170
_refine_ls_restrained_S_all      1.170
_refine_ls_shift/su_max          0.001
_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
O1 O 0.5565(6) 0.8827(4) 0.73177(10) 0.0466(8) Uani 1 1 d . . .
O2 O 0.1869(6) 1.2278(4) 0.64485(13) 0.0486(8) Uani 1 1 d . . .
O3 O 0.4627(8) 1.3940(4) 0.62594(16) 0.0713(12) Uani 1 1 d . . .
N1 N 0.3993(7) 1.2681(4) 0.64258(14) 0.0409(9) Uani 1 1 d . . .
C1 C 0.7352(8) 0.8476(5) 0.70853(14) 0.0332(9) Uani 1 1 d . . .
C2 C 0.7640(8) 0.8898(5) 0.65587(13) 0.0320(9) Uani 1 1 d . . .
H2A H 0.9225 0.9445 0.6519 0.038 Uiso 1 1 calc R . .
C3 C 0.7767(10) 0.7323(5) 0.62798(15) 0.0417(11) Uani 1 1 d . . .
H3A H 0.6197 0.6775 0.6309 0.050 Uiso 1 1 calc R . .
H3B H 0.8050 0.7541 0.5934 0.050 Uiso 1 1 calc R . .
C4 C 0.9754(10) 0.6261(5) 0.64657(16) 0.0484(12) Uani 1 1 d . . .
H4A H 0.9714 0.5259 0.6286 0.058 Uiso 1 1 calc R . .
H4B H 1.1338 0.6762 0.6405 0.058 Uiso 1 1 calc R . .
C5 C 0.9508(11) 0.5924(5) 0.69977(16) 0.0492(12) Uani 1 1 d . . .
H5A H 1.0925 0.5316 0.7109 0.059 Uiso 1 1 calc R . .
H5B H 0.8043 0.5284 0.7055 0.059 Uiso 1 1 calc R . .
C6 C 0.9330(10) 0.7464(6) 0.72858(15) 0.0459(11) Uani 1 1 d . . .
H6A H 0.8992 0.7227 0.7628 0.055 Uiso 1 1 calc R . .
H6B H 1.0887 0.8032 0.7269 0.055 Uiso 1 1 calc R . .
C7 C 0.5645(8) 0.9989(4) 0.63646(14) 0.0320(9) Uani 1 1 d . . .
H7A H 0.4048 0.9533 0.6458 0.038 Uiso 1 1 calc R . .
C8 C 0.5886(8) 1.1596(5) 0.66094(15) 0.0355(10) Uani 1 1 d . . .
H8A H 0.5714 1.1474 0.6962 0.043 Uiso 1 1 calc R . .
H8B H 0.7505 1.2038 0.6543 0.043 Uiso 1 1 calc R . .
C9 C 0.5710(9) 1.0122(5) 0.58181(14) 0.0345(9) Uani 1 1 d . . .
C10 C 0.3921(10) 0.9425(6) 0.55450(16) 0.0468(12) Uani 1 1 d . . .
H10A H 0.2605 0.8925 0.5702 0.056 Uiso 1 1 calc R . .
C11 C 0.4012(12) 0.9442(7) 0.50441(18) 0.0621(16) Uani 1 1 d . . .
H11A H 0.2783 0.8947 0.4860 0.074 Uiso 1 1 calc R . .
C12 C 0.5936(13) 1.0198(8) 0.48157(18) 0.0657(16) Uani 1 1 d . . .
H12A H 0.6028 1.0212 0.4474 0.079 Uiso 1 1 calc R . .
C13 C 0.7680(11) 1.0916(7) 0.50828(17) 0.0557(14) Uani 1 1 d . . .
H13A H 0.8966 1.1447 0.4926 0.067 Uiso 1 1 calc R . .
C14 C 0.7590(9) 1.0878(5) 0.55818(16) 0.0440(11) Uani 1 1 d . . .
H14A H 0.8827 1.1373 0.5764 0.053 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
O1 0.0423(19) 0.0526(19) 0.0449(16) 0.0033(15) 0.0106(15) 0.0063(18)
O2 0.0251(17) 0.0473(19) 0.074(2) -0.0086(18) -0.0025(16) 0.0039(15)
O3 0.057(3) 0.0292(17) 0.127(3) 0.0161(19) -0.007(2) 0.0036(19)
N1 0.037(2) 0.0307(19) 0.055(2) -0.0074(17) -0.0047(19) 0.0048(18)
C1 0.032(2) 0.029(2) 0.038(2) -0.0023(16) 0.0010(18) -0.001(2)
C2 0.028(2) 0.029(2) 0.039(2) -0.0034(16) -0.0016(17) 0.0024(19)
C3 0.055(3) 0.028(2) 0.042(2) -0.0060(17) 0.001(2) 0.012(2)
C4 0.058(3) 0.035(2) 0.052(2) -0.002(2) 0.004(2) 0.016(2)
C5 0.060(3) 0.033(2) 0.054(3) 0.004(2) -0.002(3) 0.013(3)
C6 0.045(3) 0.048(3) 0.045(2) 0.002(2) -0.005(2) 0.007(3)
C7 0.028(2) 0.0248(19) 0.043(2) -0.0015(17) 0.0010(19) 0.0008(18)
C8 0.028(2) 0.030(2) 0.049(2) -0.0048(17) -0.0037(19) 0.004(2)
C9 0.033(2) 0.0285(19) 0.041(2) -0.0036(17) -0.0019(19) 0.003(2)
C10 0.042(3) 0.051(3) 0.047(2) -0.007(2) 0.000(2) -0.004(2)
C11 0.060(4) 0.076(4) 0.050(3) -0.017(3) -0.013(3) 0.000(3)
C12 0.072(4) 0.085(4) 0.040(2) 0.000(3) -0.001(3) 0.008(4)
C13 0.059(4) 0.059(3) 0.049(3) 0.007(2) 0.004(3) 0.001(3)
C14 0.045(3) 0.043(2) 0.044(2) 0.0012(19) -0.001(2) -0.002(2)

_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
O1 C1 1.219(5) . ?
O2 N1 1.227(5) . ?
O3 N1 1.220(5) . ?
N1 C8 1.488(6) . ?
C1 C6 1.501(6) . ?
C1 C2 1.515(5) . ?
C2 C7 1.541(6) . ?
C2 C3 1.553(5) . ?
C2 H2A 1.0000 . ?
C3 C4 1.516(6) . ?
C3 H3A 0.9900 . ?
C3 H3B 0.9900 . ?
C4 C5 1.511(6) . ?
C4 H4A 0.9900 . ?
C4 H4B 0.9900 . ?
C5 C6 1.542(6) . ?
C5 H5A 0.9900 . ?
C5 H5B 0.9900 . ?
C6 H6A 0.9900 . ?
C6 H6B 0.9900 . ?
C7 C9 1.522(6) . ?
C7 C8 1.536(5) . ?
C7 H7A 1.0000 . ?
C8 H8A 0.9900 . ?
C8 H8B 0.9900 . ?
C9 C10 1.382(6) . ?
C9 C14 1.390(6) . ?
C10 C11 1.392(7) . ?
C10 H10A 0.9500 . ?
C11 C12 1.398(9) . ?
C11 H11A 0.9500 . ?
C12 C13 1.363(8) . ?
C12 H12A 0.9500 . ?
C13 C14 1.387(6) . ?
C13 H13A 0.9500 . ?
C14 H14A 0.9500 . ?

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
O3 N1 O2 122.8(4) . . ?
O3 N1 C8 118.3(4) . . ?
O2 N1 C8 118.9(4) . . ?
O1 C1 C6 122.5(4) . . ?
O1 C1 C2 122.6(4) . . ?
C6 C1 C2 114.7(4) . . ?
C1 C2 C7 113.9(3) . . ?
C1 C2 C3 106.3(3) . . ?
C7 C2 C3 112.4(3) . . ?
C1 C2 H2A 108.0 . . ?
C7 C2 H2A 108.0 . . ?
C3 C2 H2A 108.0 . . ?
C4 C3 C2 112.4(4) . . ?
C4 C3 H3A 109.1 . . ?
C2 C3 H3A 109.1 . . ?
C4 C3 H3B 109.1 . . ?
C2 C3 H3B 109.1 . . ?
H3A C3 H3B 107.9 . . ?
C5 C4 C3 112.4(4) . . ?
C5 C4 H4A 109.1 . . ?
C3 C4 H4A 109.1 . . ?
C5 C4 H4B 109.1 . . ?
C3 C4 H4B 109.1 . . ?
H4A C4 H4B 107.9 . . ?
C4 C5 C6 110.6(4) . . ?
C4 C5 H5A 109.5 . . ?
C6 C5 H5A 109.5 . . ?
C4 C5 H5B 109.5 . . ?
C6 C5 H5B 109.5 . . ?
H5A C5 H5B 108.1 . . ?
C1 C6 C5 110.1(4) . . ?
C1 C6 H6A 109.6 . . ?
C5 C6 H6A 109.6 . . ?
C1 C6 H6B 109.6 . . ?
C5 C6 H6B 109.6 . . ?
H6A C6 H6B 108.1 . . ?
C9 C7 C8 111.9(3) . . ?
C9 C7 C2 112.1(3) . . ?
C8 C7 C2 108.8(3) . . ?
C9 C7 H7A 108.0 . . ?
C8 C7 H7A 108.0 . . ?
C2 C7 H7A 108.0 . . ?
N1 C8 C7 110.0(3) . . ?
N1 C8 H8A 109.7 . . ?
C7 C8 H8A 109.7 . . ?
N1 C8 H8B 109.7 . . ?
C7 C8 H8B 109.7 . . ?
H8A C8 H8B 108.2 . . ?
C10 C9 C14 118.5(4) . . ?
C10 C9 C7 119.9(4) . . ?
C14 C9 C7 121.5(4) . . ?
C9 C10 C11 121.2(5) . . ?
C9 C10 H10A 119.4 . . ?
C11 C10 H10A 119.4 . . ?
C10 C11 C12 119.1(5) . . ?
C10 C11 H11A 120.5 . . ?
C12 C11 H11A 120.5 . . ?
C13 C12 C11 120.0(5) . . ?
C13 C12 H12A 120.0 . . ?
C11 C12 H12A 120.0 . . ?
C12 C13 C14 120.5(5) . . ?
C12 C13 H13A 119.7 . . ?
C14 C13 H13A 119.7 . . ?
C13 C14 C9 120.6(5) . . ?
C13 C14 H14A 119.7 . . ?
C9 C14 H14A 119.7 . . ?

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
O1 C1 C2 C7 7.7(6) . . . . ?
C6 C1 C2 C7 -177.8(3) . . . . ?
O1 C1 C2 C3 -116.6(5) . . . . ?
C6 C1 C2 C3 57.9(5) . . . . ?
C1 C2 C3 C4 -55.6(5) . . . . ?
C7 C2 C3 C4 179.1(4) . . . . ?
C2 C3 C4 C5 56.5(5) . . . . ?
C3 C4 C5 C6 -53.7(6) . . . . ?
O1 C1 C6 C5 116.3(5) . . . . ?
C2 C1 C6 C5 -58.2(5) . . . . ?
C4 C5 C6 C1 53.2(6) . . . . ?
C1 C2 C7 C9 -168.6(4) . . . . ?
C3 C2 C7 C9 -47.6(5) . . . . ?
C1 C2 C7 C8 67.1(5) . . . . ?
C3 C2 C7 C8 -171.9(4) . . . . ?
O3 N1 C8 C7 -125.5(4) . . . . ?
O2 N1 C8 C7 54.6(5) . . . . ?
C9 C7 C8 N1 55.1(5) . . . . ?
C2 C7 C8 N1 179.5(3) . . . . ?
C8 C7 C9 C10 -128.7(4) . . . . ?
C2 C7 C9 C10 108.8(5) . . . . ?
C8 C7 C9 C14 54.0(6) . . . . ?
C2 C7 C9 C14 -68.5(5) . . . . ?
C14 C9 C10 C11 1.4(7) . . . . ?
C7 C9 C10 C11 -175.9(5) . . . . ?
C9 C10 C11 C12 -0.9(8) . . . . ?
C10 C11 C12 C13 -0.5(9) . . . . ?
C11 C12 C13 C14 1.3(9) . . . . ?
C12 C13 C14 C9 -0.7(8) . . . . ?
C10 C9 C14 C13 -0.7(7) . . . . ?
C7 C9 C14 C13 176.7(4) . . . . ?

_diffrn_measured_fraction_theta_max 0.941
_diffrn_reflns_theta_full        27.43
_diffrn_measured_fraction_theta_full 0.941
_refine_diff_density_max         0.250
_refine_diff_density_min         -0.256
_refine_diff_density_rms         0.067


