# Supplementary Material (ESI) for Chemical Science
# This journal is (c) The Royal Society of Chemistry 2010

data_global
_journal_name_full               'Chemical Science'

_journal_coden_Cambridge         1475

_publ_contact_author_name        'Loh, Teck Peng'
_publ_contact_author_email       teckpeng@ntu.edu.sg

_publ_section_title              
;
Highly enantio-, regio- and diastereo-selective one-pot
[2 + 3]-cycloaddition reaction via isomerization of
3-butynoates to allenoates.
;
loop_
_publ_author_name
T.P.Loh
M.Sampath

# Attachment 'CIF file.txt'

data_ltp142
_database_code_depnum_ccdc_archive 'CCDC 748921'
#TrackingRef 'CIF file.txt'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C22 H20 O3'
_chemical_formula_sum            'C22 H20 O3'
_chemical_formula_weight         332.38

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   P2(1)/c

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

_cell_length_a                   10.6855(4)
_cell_length_b                   7.9692(3)
_cell_length_c                   21.0861(8)
_cell_angle_alpha                90.00
_cell_angle_beta                 102.213(2)
_cell_angle_gamma                90.00
_cell_volume                     1754.95(11)
_cell_formula_units_Z            4
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    8432
_cell_measurement_theta_min      2.47
_cell_measurement_theta_max      28.28

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.40
_exptl_crystal_size_min          0.30
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.258
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             704
_exptl_absorpt_coefficient_mu    0.083
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9637
_exptl_absorpt_correction_T_max  0.9756
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      173(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       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            25808
_diffrn_reflns_av_R_equivalents  0.0543
_diffrn_reflns_av_sigmaI/netI    0.0408
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_theta_min         1.95
_diffrn_reflns_theta_max         28.93
_reflns_number_total             4559
_reflns_number_gt                3362
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_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^)+(0.1407P)^2^+0.3118P] 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_number_reflns         4559
_refine_ls_number_parameters     227
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0795
_refine_ls_R_factor_gt           0.0572
_refine_ls_wR_factor_ref         0.2204
_refine_ls_wR_factor_gt          0.1778
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_restrained_S_all      1.078
_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 0.91503(16) 0.6829(2) 0.03254(8) 0.0264(4) Uani 1 1 d . . .
C2 C 0.84330(16) 0.8193(2) 0.05600(8) 0.0260(4) Uani 1 1 d . . .
C3 C 0.77003(17) 0.9298(2) 0.01813(8) 0.0288(4) Uani 1 1 d . . .
H3 H 0.7587 0.9311 -0.0278 0.035 Uiso 1 1 calc R . .
C4 C 0.70702(16) 1.0526(2) 0.05549(8) 0.0266(4) Uani 1 1 d . . .
H4 H 0.6120 1.0472 0.0398 0.032 Uiso 1 1 calc R . .
C5 C 0.75293(17) 1.2305(2) 0.04909(8) 0.0274(4) Uani 1 1 d . . .
H5 H 0.8446 1.2520 0.0700 0.033 Uiso 1 1 calc R . .
C6 C 0.7032(2) 1.3279(3) -0.01126(9) 0.0404(5) Uani 1 1 d . . .
H6A H 0.6384 1.2736 -0.0456 0.048 Uiso 1 1 calc R . .
H6B H 0.7635 1.4031 -0.0272 0.048 Uiso 1 1 calc R . .
C7 C 0.6640(2) 1.3751(3) 0.05026(11) 0.0442(5) Uani 1 1 d . . .
H7A H 0.5752 1.3497 0.0539 0.053 Uiso 1 1 calc R . .
H7B H 0.7003 1.4792 0.0724 0.053 Uiso 1 1 calc R . .
C8 C 0.74377(15) 0.9870(2) 0.12615(8) 0.0237(4) Uani 1 1 d . . .
H8 H 0.7820 1.0805 0.1556 0.028 Uiso 1 1 calc R . .
C9 C 0.63071(16) 0.9141(2) 0.14947(8) 0.0305(4) Uani 1 1 d . . .
C10 C 0.63204(15) 0.9128(2) 0.22075(8) 0.0236(4) Uani 1 1 d . . .
C11 C 0.53422(16) 0.8278(2) 0.24163(9) 0.0295(4) Uani 1 1 d . . .
H11 H 0.4707 0.7701 0.2111 0.035 Uiso 1 1 calc R . .
C12 C 0.52929(18) 0.8273(2) 0.30654(9) 0.0340(4) Uani 1 1 d . . .
H12 H 0.4622 0.7695 0.3205 0.041 Uiso 1 1 calc R . .
C13 C 0.62188(18) 0.9108(3) 0.35135(9) 0.0350(4) Uani 1 1 d . . .
H13 H 0.6184 0.9096 0.3960 0.042 Uiso 1 1 calc R . .
C14 C 0.71902(17) 0.9956(2) 0.33120(9) 0.0323(4) Uani 1 1 d . . .
H14 H 0.7823 1.0533 0.3619 0.039 Uiso 1 1 calc R . .
C15 C 0.72412(16) 0.9965(2) 0.26603(8) 0.0265(4) Uani 1 1 d . . .
H15 H 0.7912 1.0549 0.2523 0.032 Uiso 1 1 calc R . .
C16 C 0.84712(15) 0.8444(2) 0.12739(8) 0.0236(4) Uani 1 1 d . . .
H16 H 0.8171 0.7395 0.1455 0.028 Uiso 1 1 calc R . .
C17 C 0.97803(15) 0.8914(2) 0.16716(8) 0.0236(4) Uani 1 1 d . . .
C18 C 1.01051(17) 0.8494(2) 0.23267(8) 0.0281(4) Uani 1 1 d . . .
H18 H 0.9529 0.7851 0.2515 0.034 Uiso 1 1 calc R . .
C19 C 1.12660(19) 0.9008(2) 0.27081(10) 0.0362(4) Uani 1 1 d . . .
H19 H 1.1471 0.8736 0.3157 0.043 Uiso 1 1 calc R . .
C20 C 1.21206(18) 0.9912(2) 0.24377(10) 0.0379(5) Uani 1 1 d . . .
H20 H 1.2919 1.0252 0.2697 0.045 Uiso 1 1 calc R . .
C21 C 1.18093(19) 1.0318(3) 0.17889(11) 0.0413(5) Uani 1 1 d . . .
H21 H 1.2399 1.0937 0.1601 0.050 Uiso 1 1 calc R . .
C22 C 1.06488(18) 0.9836(2) 0.14078(9) 0.0343(4) Uani 1 1 d . . .
H22 H 1.0443 1.0138 0.0962 0.041 Uiso 1 1 calc R . .
O1 O 0.96741(12) 0.57120(16) 0.06892(6) 0.0333(3) Uani 1 1 d . . .
O2 O 0.91574(14) 0.68909(17) -0.02948(6) 0.0358(3) Uani 1 1 d . . .
H2 H 0.9537 0.6043 -0.0398 0.054 Uiso 1 1 calc R . .
O3 O 0.54172(16) 0.8535(3) 0.11140(7) 0.0659(6) Uani 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 0.0286(8) 0.0288(8) 0.0217(8) -0.0054(6) 0.0051(6) -0.0078(6)
C2 0.0307(9) 0.0259(8) 0.0223(8) -0.0060(6) 0.0079(6) -0.0073(6)
C3 0.0362(9) 0.0328(9) 0.0167(7) -0.0050(6) 0.0041(7) -0.0055(7)
C4 0.0280(8) 0.0301(9) 0.0214(8) -0.0022(6) 0.0045(6) -0.0048(6)
C5 0.0312(9) 0.0296(8) 0.0213(8) 0.0004(6) 0.0053(6) -0.0037(6)
C6 0.0468(11) 0.0390(11) 0.0295(10) 0.0067(8) -0.0049(8) -0.0127(8)
C7 0.0487(12) 0.0316(10) 0.0533(13) 0.0013(9) 0.0132(10) 0.0029(8)
C8 0.0253(8) 0.0262(8) 0.0204(8) -0.0053(6) 0.0065(6) -0.0054(6)
C9 0.0272(9) 0.0386(10) 0.0265(9) -0.0077(7) 0.0076(7) -0.0087(7)
C10 0.0236(8) 0.0227(8) 0.0257(8) -0.0015(6) 0.0079(6) 0.0008(6)
C11 0.0266(9) 0.0307(9) 0.0325(9) -0.0047(7) 0.0094(7) -0.0054(6)
C12 0.0329(10) 0.0356(10) 0.0376(10) 0.0011(8) 0.0167(8) -0.0056(7)
C13 0.0409(10) 0.0414(10) 0.0255(9) 0.0005(7) 0.0131(8) -0.0011(8)
C14 0.0329(9) 0.0383(10) 0.0250(9) -0.0023(7) 0.0046(7) -0.0058(7)
C15 0.0250(8) 0.0301(8) 0.0257(8) -0.0011(6) 0.0083(6) -0.0028(6)
C16 0.0286(8) 0.0227(8) 0.0209(8) -0.0020(6) 0.0083(6) -0.0051(6)
C17 0.0256(8) 0.0212(7) 0.0244(8) -0.0018(6) 0.0064(6) 0.0001(6)
C18 0.0347(9) 0.0230(8) 0.0261(9) 0.0014(6) 0.0054(7) 0.0018(6)
C19 0.0442(11) 0.0266(9) 0.0319(9) -0.0002(7) -0.0054(8) 0.0078(7)
C20 0.0258(9) 0.0315(9) 0.0505(12) -0.0104(8) -0.0053(8) 0.0029(7)
C21 0.0299(10) 0.0446(11) 0.0507(12) -0.0074(9) 0.0120(9) -0.0110(8)
C22 0.0354(10) 0.0404(10) 0.0285(9) -0.0021(8) 0.0099(7) -0.0099(8)
O1 0.0441(8) 0.0308(7) 0.0254(6) -0.0035(5) 0.0084(5) 0.0032(5)
O2 0.0520(9) 0.0347(7) 0.0239(6) -0.0045(5) 0.0155(6) 0.0022(6)
O3 0.0535(10) 0.1149(16) 0.0294(8) -0.0187(8) 0.0088(7) -0.0544(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 O1 1.230(2) . ?
C1 O2 1.310(2) . ?
C1 C2 1.474(2) . ?
C2 C3 1.327(3) . ?
C2 C16 1.511(2) . ?
C3 C4 1.502(2) . ?
C4 C5 1.516(2) . ?
C4 C8 1.549(2) . ?
C5 C6 1.490(2) . ?
C5 C7 1.497(3) . ?
C6 C7 1.493(3) . ?
C8 C9 1.513(2) . ?
C8 C16 1.581(2) . ?
C9 O3 1.208(2) . ?
C9 C10 1.500(2) . ?
C10 C15 1.388(2) . ?
C10 C11 1.393(2) . ?
C11 C12 1.381(3) . ?
C12 C13 1.385(3) . ?
C13 C14 1.379(2) . ?
C14 C15 1.387(2) . ?
C16 C17 1.518(2) . ?
C17 C22 1.389(2) . ?
C17 C18 1.392(2) . ?
C18 C19 1.390(3) . ?
C19 C20 1.378(3) . ?
C20 C21 1.376(3) . ?
C21 C22 1.382(3) . ?

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
O1 C1 O2 123.47(15) . . ?
O1 C1 C2 121.64(15) . . ?
O2 C1 C2 114.87(15) . . ?
C3 C2 C1 124.72(15) . . ?
C3 C2 C16 113.57(14) . . ?
C1 C2 C16 121.70(15) . . ?
C2 C3 C4 112.93(14) . . ?
C3 C4 C5 111.92(14) . . ?
C3 C4 C8 103.55(14) . . ?
C5 C4 C8 112.34(13) . . ?
C6 C5 C7 59.98(14) . . ?
C6 C5 C4 119.98(15) . . ?
C7 C5 C4 120.02(15) . . ?
C5 C6 C7 60.24(12) . . ?
C6 C7 C5 59.77(13) . . ?
C9 C8 C4 112.62(13) . . ?
C9 C8 C16 108.74(13) . . ?
C4 C8 C16 107.01(12) . . ?
O3 C9 C10 120.16(15) . . ?
O3 C9 C8 120.53(15) . . ?
C10 C9 C8 119.28(14) . . ?
C15 C10 C11 119.10(15) . . ?
C15 C10 C9 122.75(14) . . ?
C11 C10 C9 118.12(15) . . ?
C12 C11 C10 120.23(16) . . ?
C11 C12 C13 120.21(16) . . ?
C14 C13 C12 120.06(16) . . ?
C13 C14 C15 119.86(16) . . ?
C14 C15 C10 120.54(15) . . ?
C2 C16 C17 114.24(13) . . ?
C2 C16 C8 101.94(12) . . ?
C17 C16 C8 112.99(13) . . ?
C22 C17 C18 118.50(15) . . ?
C22 C17 C16 121.67(15) . . ?
C18 C17 C16 119.74(14) . . ?
C19 C18 C17 120.53(17) . . ?
C20 C19 C18 120.22(18) . . ?
C21 C20 C19 119.50(17) . . ?
C20 C21 C22 120.74(18) . . ?
C21 C22 C17 120.50(17) . . ?

_diffrn_measured_fraction_theta_max 0.984
_diffrn_reflns_theta_full        28.93
_diffrn_measured_fraction_theta_full 0.984
_refine_diff_density_max         0.334
_refine_diff_density_min         -0.348
_refine_diff_density_rms         0.084