# Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2007

data_global
_journal_name_full               Chem.Commun.

_journal_coden_Cambridge         0182

_publ_contact_author_name        'Andrew Holmes'
_publ_contact_author_address     
;
School of Chemistry
University of Melbourne
Bio21 Institute
Melbourme
Victoria
VIC 3010
AUSTRALIA
;

_publ_contact_author_email       AHOLMES@UNIMELB.EDU.AU

_publ_section_title              
;
An Organocatalytic Approach to the Core of Eunicellin
;
loop_
_publ_author_name
'Andy Holmes'
'Jonathan Burton'
'Ryan Gilmour'
'Timothy J Prior'

data_mono
_database_code_depnum_ccdc_archive 'CCDC 637637'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
(1S,2R,3S,5Z,7S,9R,10R,11Z,14S)-3-(Benzyloxy)-7-dimethyl(phenyl)silyl-
cladiella-5(6),11(12)-diene-(E)-semicarbazide
;
_chemical_name_common            
;
(1S,2R,3S,5Z,7S,9R,10R,11Z,14S)-3-(Benzyloxy)-7-
dimethyl(phenyl)silyl-cladiella-5(6),11(12)-diene-(E)-semicarbazide
;
_chemical_melting_point          ?
_chemical_formula_moiety         'C32 H41 N3 O3 Si'
_chemical_formula_sum            'C32 H41 N3 O3 Si'
_chemical_formula_weight         543.77

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'
Si Si 0.0817 0.0704 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'P 2yb'
_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                   15.630(5)
_cell_length_b                   6.649(5)
_cell_length_c                   15.862(5)
_cell_angle_alpha                90.000
_cell_angle_beta                 117.866(5)
_cell_angle_gamma                90.000
_cell_volume                     1457.3(13)
_cell_formula_units_Z            2
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    363
_cell_measurement_theta_min      8.072
_cell_measurement_theta_max      50.46

_exptl_crystal_description       plate
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.01
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.239
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             584
_exptl_absorpt_coefficient_mu    0.118
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.91
_exptl_absorpt_correction_T_max  1.00
_exptl_absorpt_process_details   
;
(SADABS; Bruker, 2004)
A correction to apply for loss of beam current with time and
absorption using a multi-scan method based on equivalents is
implemented within SADABS.
;

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.84640
_diffrn_radiation_type           synchrotron
_diffrn_radiation_source         'Daresbury SRS, Station 16.2SMX'
_diffrn_radiation_monochromator  'silicon 111'
_diffrn_measurement_device_type  'Bruker D8 diffractometer'
_diffrn_measurement_method       '\w rotation with narrow frame'
_diffrn_detector_area_resol_mean 0
_diffrn_standards_number         0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_decay_%        0
_diffrn_reflns_number            1273
_diffrn_reflns_av_R_equivalents  0.0000
_diffrn_reflns_av_sigmaI/netI    0.1390
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         4.04
_diffrn_reflns_theta_max         22.62
_reflns_number_total             1273
_reflns_number_gt                776
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'APEXII (Bruker, 2004)'
_computing_cell_refinement       'APEXII (Bruker, 2004)'
_computing_data_reduction        'APEXII (Bruker, 2004)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'WinGX v1.64 (Farrugia, 1999)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'

_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.

Diffraction data were extremely weak and were curtailed at 1.1 \%A.
(2theta
maximum 45.2 degrees)
Despite the limited data, it was possible to solve the structure by
direct
methods.
These low angle data allow a reliable determination of the atom
arrangement
but provide little information about the thermal motion of the atoms.
Only
the heavier atoms (Si, O, N) are refined with anisotropic displacement
parameters. Refining the carbon atoms in a similar way lead to
physically
unrealistic adps. Therefore all carbon atoms are treated as isotropic.

Preliminary refinements with all data (Friedel opposites not merged) led
to
an unsuitably large error on the Flack parameter. In the final
refinement
Friedel opposites were merged, hence the calculated Flack parameter is
meaningless. Using the fairly short wavelength of the synchrotron
radiation,
it is not surprising there is little amomalous dispersion in a sample
containing only light atoms.

Hydrogen atoms were placed geometrically and allowed to ride on their
atoms.

;

_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^)+(0.1403P)^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    constr
_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(9)
_refine_ls_number_reflns         1273
_refine_ls_number_parameters     193
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.1224
_refine_ls_R_factor_gt           0.0902
_refine_ls_wR_factor_ref         0.2507
_refine_ls_wR_factor_gt          0.2370
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_restrained_S_all      1.024
_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
C1 C 0.8265(12) 0.192(3) 0.7037(13) 0.051(5) Uiso 1 1 d . A .
H1 H 0.8546 0.2558 0.6665 0.061 Uiso 1 1 calc R . .
Si1 Si 0.9031(4) 0.2477(9) 0.8300(4) 0.0552(18) Uani 1 1 d . . .
C18 C 0.8666(15) 0.087(3) 0.9031(15) 0.071(7) Uiso 1 1 d . A .
H18A H 0.8005 0.1150 0.8872 0.107 Uiso 1 1 calc R . .
H18B H 0.9075 0.1149 0.9694 0.107 Uiso 1 1 calc R . .
H18C H 0.8728 -0.0519 0.8904 0.107 Uiso 1 1 calc R . .
C19 C 0.8939(13) 0.521(3) 0.8561(13) 0.052(6) Uiso 1 1 d . A .
H19A H 0.9324 0.5454 0.9232 0.078 Uiso 1 1 calc R . .
H19B H 0.8276 0.5540 0.8371 0.078 Uiso 1 1 calc R . .
H19C H 0.9171 0.6030 0.8212 0.078 Uiso 1 1 calc R . .
C20 C 1.0337(14) 0.185(4) 0.8597(14) 0.064(6) Uiso 1 1 d . A 1
C21 C 1.0850(14) 0.334(3) 0.8455(13) 0.058(6) Uiso 1 1 d . A 1
H21 H 1.0571 0.4590 0.8223 0.070 Uiso 1 1 calc R A 1
C22 C 1.1814(16) 0.294(4) 0.8671(14) 0.078(7) Uiso 1 1 d . A 1
H22 H 1.2206 0.3956 0.8634 0.094 Uiso 1 1 calc R A 1
C23 C 1.2156(17) 0.107(4) 0.8931(15) 0.076(7) Uiso 1 1 d . A 1
H23 H 1.2775 0.0753 0.9027 0.091 Uiso 1 1 calc R A 1
C24 C 1.1602(16) -0.039(4) 0.9057(16) 0.082(8) Uiso 1 1 d . A 1
H24 H 1.1855 -0.1678 0.9239 0.098 Uiso 1 1 calc R A 1
C25 C 1.0675(15) 0.001(4) 0.8917(14) 0.068(7) Uiso 1 1 d . A 1
H25 H 1.0312 -0.0944 0.9040 0.082 Uiso 1 1 calc R A 1
C2 C 0.8202(13) -0.033(3) 0.6862(13) 0.052(6) Uiso 1 1 d . . .
H2A H 0.7764 -0.0870 0.7081 0.063 Uiso 1 1 calc R A .
H2B H 0.8836 -0.0888 0.7270 0.063 Uiso 1 1 calc R . .
C3 C 0.7879(14) -0.114(4) 0.5860(14) 0.064(6) Uiso 1 1 d . A .
H3 H 0.7945 -0.2605 0.5884 0.077 Uiso 1 1 calc R . .
O1 O 0.6863(9) -0.060(2) 0.5301(8) 0.058(4) Uani 1 1 d . . .
C4 C 0.8355(14) -0.025(4) 0.5287(14) 0.062(6) Uiso 1 1 d . . .
H4 H 0.8590 0.1098 0.5536 0.074 Uiso 1 1 calc R A .
C5 C 0.9213(14) -0.148(3) 0.5389(15) 0.061(6) Uiso 1 1 d . A .
C6 C 1.0043(15) -0.174(4) 0.6407(14) 0.079(7) Uiso 1 1 d . . .
H6A H 0.9896 -0.1001 0.6844 0.118 Uiso 1 1 calc R A .
H6B H 1.0632 -0.1231 0.6438 0.118 Uiso 1 1 calc R . .
H6C H 1.0120 -0.3136 0.6576 0.118 Uiso 1 1 calc R . .
C7 C 0.9229(14) -0.236(3) 0.4653(13) 0.061(6) Uiso 1 1 d . . .
H7 H 0.9773 -0.3112 0.4765 0.073 Uiso 1 1 calc R A .
C8 C 0.8441(13) -0.223(3) 0.3659(13) 0.064(6) Uiso 1 1 d . A .
H8A H 0.8400 -0.3479 0.3329 0.076 Uiso 1 1 calc R . .
H8B H 0.8580 -0.1155 0.3326 0.076 Uiso 1 1 calc R . .
C9 C 0.7480(12) -0.181(3) 0.3658(12) 0.044(6) Uiso 1 1 d . . .
H9 H 0.7323 -0.2997 0.3927 0.053 Uiso 1 1 calc R A .
C10 C 0.6696(14) -0.162(3) 0.2618(14) 0.046(6) Uiso 1 1 d . A .
H10 H 0.6434 -0.2768 0.2256 0.056 Uiso 1 1 calc R . .
N1 N 0.6408(11) 0.005(3) 0.2255(13) 0.056(5) Uani 1 1 d . . .
N2 N 0.5752(13) 0.003(3) 0.1292(13) 0.063(5) Uani 1 1 d . A .
H2 H 0.5507 -0.1087 0.1006 0.075 Uiso 1 1 calc R . .
C11 C 0.5502(15) 0.180(4) 0.0807(18) 0.048(5) Uiso 1 1 d . . .
N3 N 0.5863(12) 0.342(3) 0.1294(11) 0.065(5) Uani 1 1 d . A .
H3A H 0.5680 0.4577 0.1026 0.078 Uiso 1 1 calc R . .
H3B H 0.6285 0.3345 0.1885 0.078 Uiso 1 1 calc R . .
O3 O 0.4883(10) 0.173(2) -0.0057(9) 0.055(4) Uani 1 1 d . A .
C12 C 0.7522(12) -0.002(3) 0.4265(13) 0.047(5) Uiso 1 1 d . A .
H12 H 0.7621 0.1210 0.3979 0.057 Uiso 1 1 calc R . .
C13 C 0.6597(12) 0.020(3) 0.4366(13) 0.041(5) Uiso 1 1 d . A .
H13 H 0.6095 -0.0667 0.3891 0.049 Uiso 1 1 calc R . .
C14 C 0.6211(13) 0.227(3) 0.4254(13) 0.049(5) Uiso 1 1 d . . .
H14 H 0.6135 0.2817 0.3649 0.058 Uiso 1 1 calc R A .
O2 O 0.5283(9) 0.199(2) 0.4183(8) 0.064(4) Uani 1 1 d . A .
C26 C 0.4694(15) 0.381(4) 0.3875(14) 0.066(6) Uiso 1 1 d . . .
H26A H 0.4139 0.3654 0.3988 0.080 Uiso 1 1 calc R A .
H26B H 0.5071 0.4941 0.4249 0.080 Uiso 1 1 calc R . .
C27 C 0.4367(13) 0.421(3) 0.2882(14) 0.051(6) Uiso 1 1 d . A .
C28 C 0.4485(15) 0.612(3) 0.2574(16) 0.065(7) Uiso 1 1 d . . .
H28 H 0.4809 0.7116 0.3022 0.078 Uiso 1 1 calc R A .
C29 C 0.4147(16) 0.652(4) 0.1666(18) 0.089(8) Uiso 1 1 d . A .
H29 H 0.4205 0.7823 0.1486 0.107 Uiso 1 1 calc R . .
C30 C 0.3712(16) 0.510(4) 0.0970(18) 0.078(7) Uiso 1 1 d . . .
H30 H 0.3524 0.5406 0.0335 0.093 Uiso 1 1 calc R A .
C31 C 0.3557(15) 0.324(3) 0.1219(15) 0.065(7) Uiso 1 1 d . A .
H31 H 0.3223 0.2280 0.0754 0.077 Uiso 1 1 calc R . .
C32 C 0.3900(14) 0.280(4) 0.2163(14) 0.068(6) Uiso 1 1 d . . .
H32 H 0.3817 0.1497 0.2332 0.082 Uiso 1 1 calc R A .
C15 C 0.6796(14) 0.374(3) 0.5042(13) 0.060(6) Uiso 1 1 d . A .
H15A H 0.7476 0.3536 0.5231 0.071 Uiso 1 1 calc R . .
H15B H 0.6631 0.5095 0.4788 0.071 Uiso 1 1 calc R . .
C16 C 0.6655(15) 0.359(3) 0.5914(14) 0.062(6) Uiso 1 1 d . . .
H16 H 0.6089 0.4141 0.5872 0.075 Uiso 1 1 calc R A .
C17 C 0.7241(13) 0.279(3) 0.6712(13) 0.052(6) Uiso 1 1 d . A .
H17 H 0.7017 0.2712 0.7160 0.063 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
Si1 0.068(4) 0.065(4) 0.036(3) 0.002(4) 0.027(3) 0.000(4)
O1 0.068(10) 0.064(11) 0.039(9) -0.003(7) 0.023(8) -0.009(8)
N1 0.060(12) 0.061(14) 0.060(14) -0.008(12) 0.040(11) 0.013(11)
N2 0.087(13) 0.060(14) 0.048(13) 0.001(11) 0.036(12) -0.007(12)
N3 0.068(13) 0.056(13) 0.047(12) 0.000(11) 0.007(10) -0.009(11)
O3 0.067(8) 0.055(10) 0.038(8) -0.013(8) 0.020(7) -0.009(8)
O2 0.074(9) 0.077(12) 0.056(8) -0.001(8) 0.043(7) -0.012(10)

_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 C2 1.52(3) . ?
C1 C17 1.54(2) . ?
C1 Si1 1.828(18) . ?
Si1 C18 1.85(2) . ?
Si1 C19 1.88(2) . ?
Si1 C20 1.91(2) . ?
C20 C25 1.34(3) . ?
C20 C21 1.36(3) . ?
C21 C22 1.41(3) . ?
C22 C23 1.34(3) . ?
C23 C24 1.38(3) . ?
C24 C25 1.38(3) . ?
C2 C3 1.52(2) . ?
C3 O1 1.46(2) . ?
C3 C4 1.54(3) . ?
O1 C13 1.44(2) . ?
C4 C5 1.51(3) . ?
C4 C12 1.54(2) . ?
C5 C7 1.32(2) . ?
C5 C6 1.54(3) . ?
C7 C8 1.48(2) . ?
C8 C9 1.53(2) . ?
C9 C12 1.52(2) . ?
C9 C10 1.53(3) . ?
C10 N1 1.23(2) . ?
N1 N2 1.39(2) . ?
N2 C11 1.36(3) . ?
C11 O3 1.26(2) . ?
C11 N3 1.29(2) . ?
C12 C13 1.53(2) . ?
C13 C14 1.48(3) . ?
C14 O2 1.41(2) . ?
C14 C15 1.51(3) . ?
O2 C26 1.46(2) . ?
C26 C27 1.43(2) . ?
C27 C32 1.39(3) . ?
C27 C28 1.41(3) . ?
C28 C29 1.31(3) . ?
C29 C30 1.37(3) . ?
C30 C31 1.35(3) . ?
C31 C32 1.37(3) . ?
C15 C16 1.50(3) . ?
C16 C17 1.28(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
C2 C1 C17 109.7(15) . . ?
C2 C1 Si1 110.7(14) . . ?
C17 C1 Si1 109.6(13) . . ?
C1 Si1 C18 109.5(10) . . ?
C1 Si1 C19 110.9(9) . . ?
C18 Si1 C19 110.0(10) . . ?
C1 Si1 C20 107.6(9) . . ?
C18 Si1 C20 109.0(10) . . ?
C19 Si1 C20 109.8(10) . . ?
C25 C20 C21 125(2) . . ?
C25 C20 Si1 118.7(17) . . ?
C21 C20 Si1 116.3(17) . . ?
C20 C21 C22 118(2) . . ?
C23 C22 C21 119(2) . . ?
C22 C23 C24 121(2) . . ?
C23 C24 C25 122(2) . . ?
C20 C25 C24 116(2) . . ?
C1 C2 C3 120.1(18) . . ?
O1 C3 C2 106.5(16) . . ?
O1 C3 C4 103.8(15) . . ?
C2 C3 C4 117.8(18) . . ?
C13 O1 C3 115.2(14) . . ?
C5 C4 C3 112.2(18) . . ?
C5 C4 C12 116.0(17) . . ?
C3 C4 C12 104.8(15) . . ?
C7 C5 C4 121.8(19) . . ?
C7 C5 C6 122(2) . . ?
C4 C5 C6 116.3(18) . . ?
C5 C7 C8 125(2) . . ?
C7 C8 C9 109.9(16) . . ?
C12 C9 C8 113.0(15) . . ?
C12 C9 C10 113.0(15) . . ?
C8 C9 C10 108.0(15) . . ?
N1 C10 C9 120.9(19) . . ?
C10 N1 N2 115.3(18) . . ?
C11 N2 N1 119(2) . . ?
O3 C11 N3 125(2) . . ?
O3 C11 N2 117(2) . . ?
N3 C11 N2 117(2) . . ?
C9 C12 C13 112.2(15) . . ?
C9 C12 C4 110.7(16) . . ?
C13 C12 C4 105.9(15) . . ?
O1 C13 C14 111.8(16) . . ?
O1 C13 C12 103.9(13) . . ?
C14 C13 C12 115.1(17) . . ?
O2 C14 C13 103.5(16) . . ?
O2 C14 C15 110.6(16) . . ?
C13 C14 C15 116.6(16) . . ?
C14 O2 C26 112.5(16) . . ?
C27 C26 O2 111.6(18) . . ?
C32 C27 C28 115(2) . . ?
C32 C27 C26 124(2) . . ?
C28 C27 C26 121(2) . . ?
C29 C28 C27 121(2) . . ?
C28 C29 C30 123(3) . . ?
C31 C30 C29 119(2) . . ?
C30 C31 C32 119(2) . . ?
C31 C32 C27 123(2) . . ?
C16 C15 C14 115.2(17) . . ?
C17 C16 C15 126(2) . . ?
C16 C17 C1 129.5(19) . . ?

_diffrn_measured_fraction_theta_max 0.993
_diffrn_reflns_theta_full        22.62
_diffrn_measured_fraction_theta_full 0.993
_refine_diff_density_max         0.273
_refine_diff_density_min         -0.329
_refine_diff_density_rms         0.073