# Supplementary Material (ESI) for Organic & Biomolecular Chemistry
# This journal is (c) The Royal Society of Chemistry 2011

data_global
_journal_name_full               Org.Biomol.Chem.

_journal_coden_Cambridge         0177
_journal_volume                  ?
_journal_page_first              ?
_journal_year                    ?

_publ_contact_author_name        'Matsubara, Seijiro'
_publ_contact_author_email       matsubar@orgrxn.mbox.media.kyoto-u.ac.jp

_publ_section_title              
;
A Tandem Reaction of Organozinc Reagent Prepared
from Palladium-catalyzed Umpolung Method: Diastereoselective Formation
of Cyclohexene Derivatives Bearing Three Adjacent Stereocenters
;
loop_
_publ_author_name
S.Matsubara
M.Sada
K.Nomura

# Attachment '4acif.txt'

data_15nm
_database_code_depnum_ccdc_archive 'CCDC 773947'
#TrackingRef '4acif.txt'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C22 H22 O4'
_chemical_formula_weight         350.40

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           Triclinic
_symmetry_space_group_name_H-M   P-1

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   6.0102(6)
_cell_length_b                   10.0194(9)
_cell_length_c                   15.9053(15)
_cell_angle_alpha                81.280(2)
_cell_angle_beta                 83.245(2)
_cell_angle_gamma                75.899(2)
_cell_volume                     914.94(15)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       ?
_exptl_crystal_colour            ?
_exptl_crystal_size_max          2
_exptl_crystal_size_mid          2
_exptl_crystal_size_min          1
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.272
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             372
_exptl_absorpt_coefficient_mu    0.087
_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  '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            5637
_diffrn_reflns_av_R_equivalents  0.0150
_diffrn_reflns_av_sigmaI/netI    0.0201
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_theta_min         2.11
_diffrn_reflns_theta_max         27.04
_reflns_number_total             3892
_reflns_number_gt                3095
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SHELXTL'
_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^)+(0.2000P)^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_number_reflns         3892
_refine_ls_number_parameters     237
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0625
_refine_ls_R_factor_gt           0.0541
_refine_ls_wR_factor_ref         0.1990
_refine_ls_wR_factor_gt          0.1829
_refine_ls_goodness_of_fit_ref   0.823
_refine_ls_restrained_S_all      0.823
_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
O4 O 0.30388(17) 0.58955(11) 0.31456(8) 0.0588(3) Uani 1 1 d . . .
H4 H 0.2338 0.5334 0.3051 0.088 Uiso 1 1 calc R . .
O3 O 0.84363(19) 0.11228(10) 0.38749(7) 0.0574(3) Uani 1 1 d . . .
O1 O 0.28016(18) 0.34503(12) 0.26119(8) 0.0633(3) Uani 1 1 d . . .
C1 C 0.6233(2) 0.38503(12) 0.30280(8) 0.0385(3) Uani 1 1 d . . .
H1 H 0.7863 0.3592 0.2822 0.046 Uiso 1 1 calc R . .
C2 C 0.4898(2) 0.31435(13) 0.25506(8) 0.0427(3) Uani 1 1 d . . .
C3 C 0.5854(2) 0.59440(13) 0.19115(9) 0.0457(3) Uani 1 1 d . . .
C4 C 0.6161(2) 0.20136(13) 0.20460(8) 0.0433(3) Uani 1 1 d . . .
C5 C 0.5415(2) 0.54578(13) 0.28588(9) 0.0436(3) Uani 1 1 d . . .
C6 C 0.6015(2) 0.33830(15) 0.39964(8) 0.0474(4) Uani 1 1 d . . .
H6 H 0.4476 0.3849 0.4218 0.057 Uiso 1 1 calc R . .
C7 C 0.8383(3) 0.19282(16) 0.16719(9) 0.0530(4) Uani 1 1 d . . .
H7 H 0.9161 0.2599 0.1734 0.064 Uiso 1 1 calc R . .
C8 C 0.8078(3) 0.57721(16) 0.15351(10) 0.0543(4) Uani 1 1 d . . .
H8 H 0.9302 0.5376 0.1868 0.065 Uiso 1 1 calc R . .
C9 C 0.6734(3) 0.60883(15) 0.33914(9) 0.0509(4) Uani 1 1 d . . .
H9 H 0.6815 0.7009 0.3234 0.061 Uiso 1 1 calc R . .
C10 C 0.6236(3) 0.18390(16) 0.42350(10) 0.0555(4) Uani 1 1 d . . .
H10A H 0.6124 0.1612 0.4851 0.067 Uiso 1 1 calc R . .
H10B H 0.5006 0.1558 0.4015 0.067 Uiso 1 1 calc R . .
C11 C 0.7756(3) 0.39285(17) 0.43983(10) 0.0565(4) Uani 1 1 d . . .
H11A H 0.7394 0.3854 0.5012 0.068 Uiso 1 1 calc R . .
H11B H 0.9283 0.3353 0.4288 0.068 Uiso 1 1 calc R . .
C12 C 0.7763(3) 0.54013(17) 0.40617(10) 0.0548(4) Uani 1 1 d . . .
H12 H 0.8551 0.5863 0.4347 0.066 Uiso 1 1 calc R . .
C13 C 0.4069(3) 0.65582(18) 0.14048(12) 0.0659(5) Uani 1 1 d . . .
H13 H 0.2556 0.6706 0.1645 0.079 Uiso 1 1 calc R . .
C14 C 0.5039(3) 0.09949(16) 0.19502(11) 0.0611(4) Uani 1 1 d . . .
H14 H 0.3536 0.1044 0.2188 0.073 Uiso 1 1 calc R . .
C15 C 0.8353(4) -0.0158(2) 0.11302(12) 0.0726(5) Uani 1 1 d . . .
H15 H 0.9091 -0.0889 0.0827 0.087 Uiso 1 1 calc R . .
C16 C 0.6158(4) -0.00962(18) 0.15001(14) 0.0769(6) Uani 1 1 d . . .
H16 H 0.5415 -0.0789 0.1449 0.092 Uiso 1 1 calc R . .
C17 C 0.9455(3) 0.08528(19) 0.12065(11) 0.0668(5) Uani 1 1 d . . .
H17 H 1.0932 0.0819 0.0945 0.080 Uiso 1 1 calc R . .
C18 C 0.8845(4) -0.02461(17) 0.39337(11) 0.0710(5) Uani 1 1 d . . .
C19 C 0.8522(3) 0.61759(19) 0.06764(11) 0.0668(5) Uani 1 1 d . . .
H19 H 1.0033 0.6061 0.0437 0.080 Uiso 1 1 calc R . .
C20 C 0.4524(4) 0.6953(2) 0.05426(14) 0.0825(6) Uani 1 1 d . . .
H20 H 0.3309 0.7365 0.0208 0.099 Uiso 1 1 calc R . .
C21 C 0.6732(4) 0.6748(2) 0.01754(13) 0.0802(6) Uani 1 1 d . . .
H21 H 0.7019 0.6994 -0.0408 0.096 Uiso 1 1 calc R . .
O2 O 0.7472(5) -0.08630(17) 0.42655(19) 0.1654(13) Uani 1 1 d . . .
C22 C 1.1107(4) -0.0865(2) 0.35224(14) 0.0843(6) Uani 1 1 d . . .
H22A H 1.1392 -0.1858 0.3639 0.126 Uiso 1 1 calc R . .
H22B H 1.2282 -0.0550 0.3743 0.126 Uiso 1 1 calc R . .
H22C H 1.1123 -0.0591 0.2917 0.126 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
O4 0.0406(6) 0.0464(6) 0.0869(8) -0.0189(5) 0.0003(5) -0.0011(4)
O3 0.0617(7) 0.0384(6) 0.0674(7) 0.0010(4) -0.0052(5) -0.0076(5)
O1 0.0400(6) 0.0585(7) 0.0967(9) -0.0219(6) -0.0099(5) -0.0121(5)
C1 0.0352(6) 0.0339(6) 0.0468(7) -0.0083(5) -0.0042(5) -0.0061(5)
C2 0.0398(7) 0.0374(7) 0.0519(7) -0.0030(5) -0.0072(5) -0.0107(5)
C3 0.0472(8) 0.0331(7) 0.0594(8) -0.0029(5) -0.0143(6) -0.0113(5)
C4 0.0503(8) 0.0377(7) 0.0449(7) -0.0038(5) -0.0130(5) -0.0124(5)
C5 0.0389(7) 0.0353(7) 0.0569(8) -0.0105(5) -0.0076(5) -0.0048(5)
C6 0.0477(8) 0.0465(8) 0.0472(7) -0.0091(6) 0.0002(6) -0.0091(6)
C7 0.0528(8) 0.0552(8) 0.0559(8) -0.0185(6) -0.0037(6) -0.0155(6)
C8 0.0535(9) 0.0526(9) 0.0587(9) -0.0023(6) -0.0131(6) -0.0145(6)
C9 0.0536(8) 0.0419(7) 0.0618(9) -0.0188(6) -0.0042(6) -0.0129(6)
C10 0.0604(9) 0.0527(9) 0.0511(8) 0.0015(6) 0.0002(6) -0.0157(7)
C11 0.0649(10) 0.0575(9) 0.0485(8) -0.0113(6) -0.0134(7) -0.0103(7)
C12 0.0560(9) 0.0576(9) 0.0576(8) -0.0232(7) -0.0061(7) -0.0156(7)
C13 0.0557(10) 0.0586(10) 0.0843(12) 0.0118(8) -0.0276(8) -0.0176(7)
C14 0.0676(10) 0.0506(9) 0.0740(10) -0.0134(7) -0.0096(8) -0.0253(7)
C15 0.0938(14) 0.0554(10) 0.0712(11) -0.0271(8) -0.0137(10) -0.0075(9)
C16 0.1004(15) 0.0508(10) 0.0928(14) -0.0243(9) -0.0174(11) -0.0290(10)
C17 0.0675(11) 0.0718(11) 0.0627(10) -0.0280(8) -0.0030(8) -0.0085(8)
C18 0.0975(14) 0.0410(8) 0.0693(11) 0.0010(7) 0.0054(9) -0.0166(9)
C19 0.0741(12) 0.0704(11) 0.0619(10) -0.0023(8) -0.0076(8) -0.0310(9)
C20 0.0862(14) 0.0825(13) 0.0850(13) 0.0259(10) -0.0470(11) -0.0349(11)
C21 0.1087(16) 0.0828(13) 0.0611(10) 0.0143(9) -0.0269(10) -0.0497(12)
O2 0.176(2) 0.0549(9) 0.245(3) -0.0244(12) 0.111(2) -0.0447(12)
C22 0.1021(16) 0.0497(10) 0.0860(13) -0.0019(9) 0.0009(11) 0.0031(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
O4 C5 1.4291(15) . ?
O3 C18 1.324(2) . ?
O3 C10 1.4410(19) . ?
O1 C2 1.2177(16) . ?
C1 C2 1.5184(17) . ?
C1 C6 1.5404(18) . ?
C1 C5 1.5563(17) . ?
C2 C4 1.4885(19) . ?
C3 C8 1.380(2) . ?
C3 C13 1.382(2) . ?
C3 C5 1.5243(19) . ?
C4 C7 1.385(2) . ?
C4 C14 1.3880(19) . ?
C5 C9 1.5196(18) . ?
C6 C10 1.513(2) . ?
C6 C11 1.531(2) . ?
C7 C17 1.384(2) . ?
C8 C19 1.378(2) . ?
C9 C12 1.311(2) . ?
C11 C12 1.492(2) . ?
C13 C20 1.383(3) . ?
C14 C16 1.388(3) . ?
C15 C16 1.371(3) . ?
C15 C17 1.365(3) . ?
C18 O2 1.178(2) . ?
C18 C22 1.471(3) . ?
C19 C21 1.372(3) . ?
C20 C21 1.366(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
C18 O3 C10 117.38(13) . . ?
C2 C1 C6 111.67(10) . . ?
C2 C1 C5 111.31(10) . . ?
C6 C1 C5 109.22(10) . . ?
O1 C2 C4 119.94(12) . . ?
O1 C2 C1 120.35(12) . . ?
C4 C2 C1 119.61(11) . . ?
C8 C3 C13 118.07(15) . . ?
C8 C3 C5 120.19(12) . . ?
C13 C3 C5 121.74(14) . . ?
C7 C4 C14 118.71(14) . . ?
C7 C4 C2 123.49(12) . . ?
C14 C4 C2 117.80(13) . . ?
O4 C5 C9 106.13(11) . . ?
O4 C5 C3 111.29(11) . . ?
C9 C5 C3 110.75(11) . . ?
O4 C5 C1 110.68(10) . . ?
C9 C5 C1 108.28(11) . . ?
C3 C5 C1 109.61(10) . . ?
C10 C6 C1 114.21(11) . . ?
C10 C6 C11 112.94(12) . . ?
C1 C6 C11 107.70(11) . . ?
C17 C7 C4 120.57(15) . . ?
C19 C8 C3 121.38(15) . . ?
C12 C9 C5 123.37(13) . . ?
O3 C10 C6 108.44(11) . . ?
C12 C11 C6 112.61(12) . . ?
C9 C12 C11 124.44(13) . . ?
C3 C13 C20 120.29(18) . . ?
C16 C14 C4 120.04(17) . . ?
C16 C15 C17 120.05(16) . . ?
C14 C16 C15 120.37(16) . . ?
C15 C17 C7 120.23(18) . . ?
O2 C18 O3 121.75(19) . . ?
O2 C18 C22 125.40(18) . . ?
O3 C18 C22 112.81(16) . . ?
C8 C19 C21 119.96(19) . . ?
C21 C20 C13 120.96(16) . . ?
C20 C21 C19 119.30(18) . . ?

_diffrn_measured_fraction_theta_max 0.968
_diffrn_reflns_theta_full        27.04
_diffrn_measured_fraction_theta_full 0.968
_refine_diff_density_max         0.389
_refine_diff_density_min         -0.262
_refine_diff_density_rms         0.051