# Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2005

data_global

_journal_coden_Cambridge         182

loop_
_publ_author_name
'C. Willis'
'Conor Barry'
'Nick Bushby'
'Jonathan P. H. Charmant'
'Jon D. Elsworth'
'John R. Harding'

_publ_contact_author_name        'C. Willis'
_publ_contact_author_address     
;
School of Chemistry
University of Bristol
Cantock's Close
Bristol
BS8 1TS
UNITED KINGDOM
;

_publ_contact_author_email       CHRIS.WILLIS@BRIS.AC.UK

_publ_requested_journal          'Chemical Communications'

_publ_section_title              
;
Total synthesis of a diastereomer of the marine
natural product clavosolide A
;

data_11
_database_code_depnum_ccdc_archive 'CCDC 280355'

_audit_creation_method           SHELXL-97

_chemical_formula_moiety         'C28 H44 O8, 2(H2 O)'
_chemical_formula_sum            'C28 H48 O10'
_chemical_formula_weight         544.66
_chemical_absolute_configuration syn

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'
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   'C 2'
_symmetry_space_group_name_Hall  'C 2y'

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

_cell_length_a                   20.351(4)
_cell_length_b                   8.8020(18)
_cell_length_c                   8.8390(18)
_cell_angle_alpha                90.00
_cell_angle_beta                 100.07(3)
_cell_angle_gamma                90.00
_cell_volume                     1558.9(6)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    4997
_cell_measurement_theta_min      2.34
_cell_measurement_theta_max      27.30

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_exptl_crystal_density_diffrn    1.160
_exptl_crystal_density_method    none
_exptl_crystal_F_000             592
_exptl_absorpt_coefficient_mu    0.087
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.917
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_process_details   'SADABS v2.03 (Sheldrick, 2003)'

_exptl_special_details           
;
During optical inspection, the crystal did not fully extinguish plane
polarised light. Indexing indicated that a superlattice might be present with
doubling of the a and b axes but the intensities of the superlattice spots
were very weak. Some atoms have elongated thermal elipsoids. Splitting these
atoms does not produce disordered fragments with sensible geometries.
;

_diffrn_ambient_temperature      100(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  'CCD area detector'
_diffrn_measurement_method       'Frames, each covering 0.3 \% in \w'
_diffrn_detector_area_resol_mean 8.366
_diffrn_standards_decay_%        0
_diffrn_reflns_number            12594
_diffrn_reflns_av_R_equivalents  0.0249
_diffrn_reflns_av_sigmaI/netI    0.0158
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         2.03
_diffrn_reflns_theta_max         27.52
_reflns_number_total             1919
_reflns_number_gt                1896
_reflns_threshold_expression     >2\s(I)

_computing_data_collection       'SMART v5.628 (Bruker-AXS, 2003)'
_computing_cell_refinement       'SAINT v6.28A (Bruker-AXS, 2000)'
_computing_data_reduction        
;
SAINT v6.28A and SHELXTL v6.1 (Bruker-AXS, 2000)
;
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'SHELXTL v6.1 (Bruker-AXS, 2000)'
_computing_publication_material  'SHELXTL v6.1 (Bruker-AXS, 2000)'

_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^)+(0.0581P)^2^+2.4450P] 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_number_reflns         1919
_refine_ls_number_parameters     181
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0594
_refine_ls_R_factor_gt           0.0589
_refine_ls_wR_factor_ref         0.1447
_refine_ls_wR_factor_gt          0.1444
_refine_ls_goodness_of_fit_ref   1.111
_refine_ls_restrained_S_all      1.111
_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 0.58758(15) 0.7983(5) 0.2259(4) 0.0395(10) Uani 1 1 d . . .
H1A H 0.6303 0.8506 0.2216 0.047 Uiso 1 1 calc R . .
H1B H 0.5740 0.7421 0.1284 0.047 Uiso 1 1 calc R . .
C2 C 0.59686(14) 0.6882(4) 0.3596(4) 0.0301(7) Uani 1 1 d . . .
H2A H 0.5537 0.6344 0.3612 0.036 Uiso 1 1 calc R . .
C3 C 0.65165(16) 0.5698(5) 0.3549(6) 0.0479(12) Uani 1 1 d . . .
H3 H 0.6940 0.6244 0.3472 0.058 Uiso 1 1 calc R . .
C4 C 0.66277(17) 0.4768(4) 0.5043(7) 0.0577(15) Uani 1 1 d . . .
H4 H 0.6232 0.4100 0.5062 0.069 Uiso 1 1 calc R . .
C5 C 0.67269(16) 0.5778(4) 0.6427(5) 0.0424(10) Uani 1 1 d . . .
H5A H 0.7168 0.6279 0.6525 0.051 Uiso 1 1 calc R . .
H5B H 0.6728 0.5151 0.7356 0.051 Uiso 1 1 calc R . .
C6 C 0.61865(14) 0.6991(4) 0.6343(4) 0.0270(7) Uani 1 1 d . . .
H6 H 0.5751 0.6500 0.6426 0.032 Uiso 1 1 calc R . .
C7 C 0.63607(14) 0.8136(4) 0.7600(3) 0.0292(7) Uani 1 1 d . . .
H7A H 0.6786 0.8629 0.7483 0.035 Uiso 1 1 calc R . .
H7B H 0.6437 0.7594 0.8596 0.035 Uiso 1 1 calc R . .
C8 C 0.58426(14) 0.9367(4) 0.7658(3) 0.0292(7) Uani 1 1 d . . .
H8 H 0.5722 0.9858 0.6627 0.035 Uiso 1 1 calc R . .
C9 C 0.46514(15) 0.9135(5) 0.7551(3) 0.0319(8) Uani 1 1 d . . .
C10 C 0.60927(17) 1.0544(7) 0.8846(4) 0.0476(12) Uani 1 1 d . . .
H10 H 0.6221 1.0151 0.9918 0.057 Uiso 1 1 calc R . .
C11 C 0.5852(2) 1.2151(8) 0.8722(8) 0.089(2) Uani 1 1 d . . .
H11A H 0.5504 1.2423 0.7834 0.107 Uiso 1 1 calc R . .
H11B H 0.5821 1.2698 0.9686 0.107 Uiso 1 1 calc R . .
C12 C 0.65289(18) 1.1767(5) 0.8416(5) 0.0462(11) Uani 1 1 d . . .
H12 H 0.6572 1.1780 0.7306 0.055 Uiso 1 1 calc R . .
C13 C 0.71590(19) 1.2208(7) 0.9519(5) 0.0559(13) Uani 1 1 d . . .
H13A H 0.7087 1.2082 1.0579 0.084 Uiso 1 1 calc R . .
H13B H 0.7268 1.3271 0.9346 0.084 Uiso 1 1 calc R . .
H13C H 0.7529 1.1556 0.9342 0.084 Uiso 1 1 calc R . .
C14 C 0.6340(2) 0.4656(7) 0.2151(8) 0.095(3) Uani 1 1 d . . .
H14A H 0.6367 0.5230 0.1214 0.142 Uiso 1 1 calc R . .
H14B H 0.5885 0.4267 0.2100 0.142 Uiso 1 1 calc R . .
H14C H 0.6654 0.3804 0.2244 0.142 Uiso 1 1 calc R . .
O1 O 0.61224(9) 0.7803(2) 0.4930(2) 0.0205(4) Uani 1 1 d . . .
O2 O 0.72112(12) 0.3843(3) 0.5108(7) 0.0889(16) Uani 1 1 d . . .
H2 H 0.7101 0.2922 0.5069 0.133 Uiso 1 1 calc R . .
O3 O 0.45534(11) 1.0370(3) 0.6989(3) 0.0353(6) Uani 1 1 d . . .
O4 O 0.52609(10) 0.8542(4) 0.8033(2) 0.0354(6) Uani 1 1 d . . .
O5 O 0.67515(12) 0.1002(3) 0.4579(4) 0.0371(6) Uani 1 1 d . . .
H5C H 0.698(3) 0.025(7) 0.458(6) 0.056 Uiso 1 1 d . . .
H5D H 0.637(3) 0.065(6) 0.412(5) 0.056 Uiso 1 1 d . . .

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 0.0207(14) 0.073(3) 0.0262(15) -0.0190(18) 0.0083(11) -0.0119(17)
C2 0.0151(13) 0.0287(17) 0.0481(19) -0.0202(15) 0.0105(12) -0.0040(12)
C3 0.0181(14) 0.038(2) 0.090(3) -0.045(2) 0.0172(17) -0.0082(15)
C4 0.0172(15) 0.0119(14) 0.147(5) -0.010(2) 0.024(2) -0.0007(13)
C5 0.0209(14) 0.0211(17) 0.087(3) 0.0225(17) 0.0150(16) 0.0067(13)
C6 0.0166(12) 0.0201(14) 0.0452(17) 0.0131(14) 0.0083(12) 0.0045(11)
C7 0.0176(13) 0.044(2) 0.0261(13) 0.0140(14) 0.0028(10) 0.0081(13)
C8 0.0182(13) 0.049(2) 0.0195(12) -0.0021(14) 0.0015(10) 0.0077(14)
C9 0.0207(14) 0.058(2) 0.0163(12) -0.0049(14) 0.0012(10) 0.0080(15)
C10 0.0230(15) 0.092(3) 0.0263(15) -0.028(2) -0.0009(12) 0.0042(19)
C11 0.030(2) 0.108(5) 0.116(4) -0.092(4) -0.023(2) 0.024(3)
C12 0.0305(18) 0.053(2) 0.048(2) -0.0306(19) -0.0135(15) 0.0119(18)
C13 0.0323(19) 0.074(3) 0.054(2) -0.036(2) -0.0111(17) 0.009(2)
C14 0.037(2) 0.096(4) 0.155(6) -0.107(5) 0.027(3) -0.014(3)
O1 0.0195(9) 0.0152(9) 0.0271(10) -0.0044(8) 0.0046(7) 0.0002(8)
O2 0.0171(11) 0.0137(12) 0.240(5) -0.021(2) 0.033(2) -0.0016(10)
O3 0.0207(11) 0.0437(15) 0.0386(12) -0.0122(12) -0.0033(9) 0.0054(11)
O4 0.0176(9) 0.0657(18) 0.0230(10) 0.0055(11) 0.0040(8) 0.0086(11)
O5 0.0177(11) 0.0155(11) 0.0757(18) -0.0050(12) 0.0013(11) -0.0014(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
C1 C9 1.507(5) 2_656 ?
C1 C2 1.514(6) . ?
C1 H1A 0.9900 . ?
C1 H1B 0.9900 . ?
C2 O1 1.421(4) . ?
C2 C3 1.532(4) . ?
C2 H2A 1.0000 . ?
C3 C14 1.531(5) . ?
C3 C4 1.536(7) . ?
C3 H3 1.0000 . ?
C4 O2 1.433(4) . ?
C4 C5 1.496(7) . ?
C4 H4 1.0000 . ?
C5 C6 1.525(4) . ?
C5 H5A 0.9900 . ?
C5 H5B 0.9900 . ?
C6 O1 1.425(4) . ?
C6 C7 1.496(5) . ?
C6 H6 1.0000 . ?
C7 C8 1.519(4) . ?
C7 H7A 0.9900 . ?
C7 H7B 0.9900 . ?
C8 O4 1.475(4) . ?
C8 C10 1.499(5) . ?
C8 H8 1.0000 . ?
C9 O3 1.198(5) . ?
C9 O4 1.344(4) . ?
C9 C1 1.507(5) 2_656 ?
C10 C12 1.486(7) . ?
C10 C11 1.495(8) . ?
C10 H10 1.0000 . ?
C11 C12 1.489(6) . ?
C11 H11A 0.9900 . ?
C11 H11B 0.9900 . ?
C12 C13 1.519(5) . ?
C12 H12 1.0000 . ?
C13 H13A 0.9800 . ?
C13 H13B 0.9800 . ?
C13 H13C 0.9800 . ?
C14 H14A 0.9800 . ?
C14 H14B 0.9800 . ?
C14 H14C 0.9800 . ?
O2 H2 0.8400 . ?
O5 H5C 0.80(6) . ?
O5 H5D 0.88(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
C9 C1 C2 109.7(2) 2_656 . ?
C9 C1 H1A 109.7 2_656 . ?
C2 C1 H1A 109.7 . . ?
C9 C1 H1B 109.7 2_656 . ?
C2 C1 H1B 109.7 . . ?
H1A C1 H1B 108.2 . . ?
O1 C2 C1 105.2(3) . . ?
O1 C2 C3 110.8(3) . . ?
C1 C2 C3 114.0(3) . . ?
O1 C2 H2A 108.9 . . ?
C1 C2 H2A 108.9 . . ?
C3 C2 H2A 108.9 . . ?
C14 C3 C2 111.1(4) . . ?
C14 C3 C4 110.7(4) . . ?
C2 C3 C4 109.7(3) . . ?
C14 C3 H3 108.4 . . ?
C2 C3 H3 108.4 . . ?
C4 C3 H3 108.4 . . ?
O2 C4 C5 108.2(4) . . ?
O2 C4 C3 109.5(4) . . ?
C5 C4 C3 111.4(3) . . ?
O2 C4 H4 109.2 . . ?
C5 C4 H4 109.2 . . ?
C3 C4 H4 109.2 . . ?
C4 C5 C6 112.5(3) . . ?
C4 C5 H5A 109.1 . . ?
C6 C5 H5A 109.1 . . ?
C4 C5 H5B 109.1 . . ?
C6 C5 H5B 109.1 . . ?
H5A C5 H5B 107.8 . . ?
O1 C6 C7 106.6(2) . . ?
O1 C6 C5 110.4(3) . . ?
C7 C6 C5 111.1(3) . . ?
O1 C6 H6 109.6 . . ?
C7 C6 H6 109.6 . . ?
C5 C6 H6 109.6 . . ?
C6 C7 C8 115.5(2) . . ?
C6 C7 H7A 108.4 . . ?
C8 C7 H7A 108.4 . . ?
C6 C7 H7B 108.4 . . ?
C8 C7 H7B 108.4 . . ?
H7A C7 H7B 107.5 . . ?
O4 C8 C10 111.8(3) . . ?
O4 C8 C7 104.2(3) . . ?
C10 C8 C7 111.3(3) . . ?
O4 C8 H8 109.8 . . ?
C10 C8 H8 109.8 . . ?
C7 C8 H8 109.8 . . ?
O3 C9 O4 124.1(3) . . ?
O3 C9 C1 126.0(3) . 2_656 ?
O4 C9 C1 109.8(3) . 2_656 ?
C12 C10 C11 60.0(4) . . ?
C12 C10 C8 117.8(3) . . ?
C11 C10 C8 122.4(3) . . ?
C12 C10 H10 115.1 . . ?
C11 C10 H10 115.1 . . ?
C8 C10 H10 115.1 . . ?
C12 C11 C10 59.7(3) . . ?
C12 C11 H11A 117.8 . . ?
C10 C11 H11A 117.8 . . ?
C12 C11 H11B 117.8 . . ?
C10 C11 H11B 117.8 . . ?
H11A C11 H11B 114.9 . . ?
C10 C12 C11 60.3(4) . . ?
C10 C12 C13 119.8(4) . . ?
C11 C12 C13 122.0(3) . . ?
C10 C12 H12 114.7 . . ?
C11 C12 H12 114.7 . . ?
C13 C12 H12 114.7 . . ?
C12 C13 H13A 109.5 . . ?
C12 C13 H13B 109.5 . . ?
H13A C13 H13B 109.5 . . ?
C12 C13 H13C 109.5 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
C3 C14 H14A 109.5 . . ?
C3 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
C3 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C2 O1 C6 114.5(2) . . ?
C4 O2 H2 109.5 . . ?
C9 O4 C8 118.1(3) . . ?
H5C O5 H5D 100(5) . . ?

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
C9 C1 C2 O1 -56.0(3) 2_656 . . . ?
C9 C1 C2 C3 -177.6(3) 2_656 . . . ?
O1 C2 C3 C14 177.5(4) . . . . ?
C1 C2 C3 C14 -64.1(5) . . . . ?
O1 C2 C3 C4 54.8(3) . . . . ?
C1 C2 C3 C4 173.2(3) . . . . ?
C14 C3 C4 O2 66.6(4) . . . . ?
C2 C3 C4 O2 -170.4(3) . . . . ?
C14 C3 C4 C5 -173.8(3) . . . . ?
C2 C3 C4 C5 -50.8(3) . . . . ?
O2 C4 C5 C6 170.6(3) . . . . ?
C3 C4 C5 C6 50.2(4) . . . . ?
C4 C5 C6 O1 -52.3(4) . . . . ?
C4 C5 C6 C7 -170.4(3) . . . . ?
O1 C6 C7 C8 61.8(3) . . . . ?
C5 C6 C7 C8 -177.9(3) . . . . ?
C6 C7 C8 O4 65.3(3) . . . . ?
C6 C7 C8 C10 -174.1(3) . . . . ?
O4 C8 C10 C12 -161.7(3) . . . . ?
C7 C8 C10 C12 82.2(4) . . . . ?
O4 C8 C10 C11 -91.3(5) . . . . ?
C7 C8 C10 C11 152.6(4) . . . . ?
C8 C10 C11 C12 -105.7(4) . . . . ?
C8 C10 C12 C11 113.3(4) . . . . ?
C11 C10 C12 C13 112.1(4) . . . . ?
C8 C10 C12 C13 -134.6(4) . . . . ?
C10 C11 C12 C13 -108.5(5) . . . . ?
C1 C2 O1 C6 176.0(2) . . . . ?
C3 C2 O1 C6 -60.4(3) . . . . ?
C7 C6 O1 C2 178.9(2) . . . . ?
C5 C6 O1 C2 58.1(3) . . . . ?
O3 C9 O4 C8 -8.7(4) . . . . ?
C1 C9 O4 C8 167.9(3) 2_656 . . . ?
C10 C8 O4 C9 87.3(4) . . . . ?
C7 C8 O4 C9 -152.4(3) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O2 H2 O5 0.84 1.86 2.682(4) 167.8 .
O5 H5C O2 0.80(6) 2.05(6) 2.818(4) 161(5) 4_646
O5 H5D O3 0.88(5) 1.97(5) 2.827(3) 166(5) 2_646

_diffrn_measured_fraction_theta_max 1.000
_diffrn_reflns_theta_full        27.52
_diffrn_measured_fraction_theta_full 1.000
_refine_diff_density_max         0.704
_refine_diff_density_min         -0.464
_refine_diff_density_rms         0.053