# Supplementary Material (ESI) for Chemical Communications
# This journal is (c) The Royal Society of Chemistry 2006

data_global

_journal_coden_Cambridge         182

loop_
_publ_author_name
'Hans-Joachim Knolker'
'Elke Baum'
'Regina Czerwonka'
'Kethiri R. Reddy'

_publ_contact_author_name        'Hans-Joachim Knolker'
_publ_contact_author_address     
;
Institut fur Organische Chemie
Technische Universitat Dresden
Bergstrasse 66
Dresden
01069
GERMANY
;

_publ_contact_author_email       HANS-JOACHIM.KNOELKER@CHEMIE.TU-DRESDEN.DE

_publ_requested_journal          'Chemical Communications'

_publ_section_title              
;
First enantioselective total synthesis of
neocarazostatin B, determination of its absolute configuration and
transformation into carquinostatin A
;

# Attachment 'eba18.cif'

data_eba18
_database_code_depnum_ccdc_archive 'CCDC 289105'

_audit_creation_method           SHELXL
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_formula_moiety         ?
_chemical_formula_structural     ?
_chemical_formula_analytical     ?
_chemical_formula_sum            'C21 H22 Br N O5'
_chemical_formula_weight         448.31
_chemical_melting_point          ?
_chemical_compound_source        ?

_computing_data_collection       'STADI4 (STOE, 1996)'
_computing_cell_refinement       'STADI4 (STOE, 1996)'
_computing_data_reduction        'X-RED (STOE, 1996)'

_cell_length_a                   11.2163(8)
_cell_length_b                   8.5454(8)
_cell_length_c                   11.5523(12)
_cell_angle_alpha                90.00
_cell_angle_beta                 112.480(6)
_cell_angle_gamma                90.00
_cell_volume                     1023.12(12)
_cell_formula_units              1.0
_cell_measurement_temperature    218(1)
_cell_measurement_reflns_used    36
_cell_measurement_theta_min      13.5
_cell_measurement_theta_max      16.5
_cell_special_details            
; ?
;

_exptl_crystal_description       fragment
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          1.200
_exptl_crystal_size_mid          1.133
_exptl_crystal_size_min          1.000
#_exptl_crystal_density_diffrn 0.000
_exptl_crystal_density_meas      ?

_diffrn_measurement_device       'STOE STADI4 4-circle-diffractometer'
_diffrn_measurement_method       
; Scan width (omega) = 1.32 - 1.52, scan ratio 2theta:omega = 0.00
I(Net) and sigma(I) calculated according to Blessing (1987)
;
_diffrn_special_details          ?
_diffrn_ambient_environment      'dry air'
_diffrn_ambient_temperature      218(1)
_diffrn_radiation_collimation    '0.8 mm'
_diffrn_radiation_detector       'NaI(Tl) scintillation counter'
_diffrn_radiation_monochromator  'planar graphite'
_diffrn_radiation_polarisn_norm  90
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_standards_number         3
_diffrn_standards_interval_time  120
_diffrn_standards_decay_%        3.2

_diffrn_reflns_number            2518
_diffrn_reflns_theta_min         1.91
_diffrn_reflns_theta_max         27.50
_diffrn_reflns_av_sigmaI/netI    0.0132
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_limit_l_max       14

_reflns_d_resolution_high        0.770
_reflns_d_resolution_low         10.661
_reflns_limit_h_min              -14
_reflns_limit_h_max              13
_reflns_limit_k_min              0
_reflns_limit_k_max              10
_reflns_limit_l_min              -13
_reflns_limit_l_max              14

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C .0033 .0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H .0000 .0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N .0061 .0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O .0106 .0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   P21

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

_exptl_crystal_density_diffrn    1.455
_exptl_crystal_F_000             460
_exptl_absorpt_coefficient_mu    2.040
_exptl_absorpt_correction_type   none

_exptl_special_details           
;
?
;

_reflns_number_total             2237
_reflns_number_observed          2144
_reflns_observed_criterion       >2sigma(I)

_computing_structure_solution    'SHELXS-86 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-93 (Sheldrick, 1993)'
_computing_molecular_graphics    SCHAKAL
_computing_publication_material  ?

_refine_special_details          
;
Refinement on F^2^ for ALL reflections except for 2 with very negative F^2^
or flagged by the user for potential systematic errors. Weighted R-factors
wR and all goodnesses 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 observed criterion
of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[s^2^(Fo^2^)+( 0.0481P)^2^+0.3102P] 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    refall
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.0572(35)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^l^3^/sin(2q)]^-1/4^
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.002(9)
_refine_ls_number_reflns         2235
_refine_ls_number_parameters     342
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0307
_refine_ls_R_factor_obs          0.0279
_refine_ls_wR_factor_all         0.0749
_refine_ls_wR_factor_obs         0.0710
_refine_ls_goodness_of_fit_all   1.109
_refine_ls_goodness_of_fit_obs   1.088
_refine_ls_restrained_S_all      1.118
_refine_ls_restrained_S_obs      1.088
_refine_ls_shift/esd_max         -0.010
_refine_ls_shift/esd_mean        0.001

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_thermal_displace_type
_atom_site_occupancy
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_group
Br Br 0.78271(3) 0.78324(5) 0.24488(3) 0.0453(2) Uani 1 d . .
C1 C 0.9520(3) 0.8640(5) 0.3319(3) 0.0350(7) Uani 1 d . .
C2 C 0.9962(3) 0.8783(5) 0.4626(3) 0.0376(8) Uani 1 d . .
H2 H 0.9493(34) 0.8407(44) 0.5094(33) 0.024(9) Uiso 1 d . .
C3 C 1.1168(3) 0.9404(5) 0.5297(3) 0.0347(8) Uani 1 d . .
H3 H 1.1518(44) 0.9479(61) 0.6251(41) 0.049(12) Uiso 1 d . .
C4 C 1.1925(3) 0.9858(4) 0.4637(3) 0.0283(7) Uani 1 d . .
C5 C 1.1489(3) 0.9674(4) 0.3319(3) 0.0273(6) Uani 1 d . .
C6 C 1.0257(3) 0.9067(5) 0.2647(3) 0.0331(7) Uani 1 d . .
H6 H 0.9911(43) 0.8897(60) 0.1778(44) 0.041(11) Uiso 1 d . .
N N 1.3155(3) 1.0471(4) 0.5081(2) 0.0290(6) Uani 1 d . .
H1 H 1.3625(51) 1.0688(69) 0.5909(49) 0.059(14) Uiso 1 d . .
C7 C 1.2531(3) 1.0191(4) 0.2977(3) 0.0269(6) Uani 1 d . .
C8 C 1.2726(3) 1.0291(4) 0.1872(3) 0.0298(7) Uani 1 d . .
C9 C 1.3885(3) 1.0868(5) 0.1861(3) 0.0307(7) Uani 1 d . .
C10 C 1.4889(3) 1.1338(4) 0.2976(3) 0.0306(7) Uani 1 d . .
C11 C 1.4723(3) 1.1252(4) 0.4116(3) 0.0262(7) Uani 1 d . .
C12 C 1.3546(4) 1.0678(4) 0.4087(3) 0.0268(7) Uani 1 d . .
O1 O 1.1798(2) 0.9714(3) 0.0750(2) 0.0330(5) Uani 1 d . .
O2 O 1.1013(3) 1.2123(4) 0.0181(3) 0.0585(8) Uani 1 d . .
C13 C 1.1031(3) 1.0778(5) -0.0074(3) 0.0371(8) Uani 1 d . .
C14 C 1.0270(4) 1.0006(7) -0.1293(4) 0.0514(11) Uani 1 d . .
H14A H 1.0887(72) 0.9774(110) -0.1669(63) 0.103(23) Uiso 1 d . .
H14B H 0.9848(68) 1.0866(96) -0.1805(66) 0.086(20) Uiso 1 d . .
H14C H 0.9797(54) 0.9368(74) -0.0996(48) 0.061(15) Uiso 1 d . .
O3 O 1.4024(3) 1.1046(4) 0.0732(2) 0.0437(6) Uani 1 d . .
C15 C 1.4309(5) 0.9628(7) 0.0231(4) 0.0550(12) Uani 1 d . .
H15A H 1.3574(80) 0.8740(110) 0.0077(69) 0.108(26) Uiso 1 d . .
H15B H 1.5037(65) 0.9259(84) 0.0761(57) 0.073(18) Uiso 1 d . .
H15C H 1.4565(54) 0.9821(79) -0.0510(53) 0.072(17) Uiso 1 d . .
C16 C 1.6109(4) 1.1940(6) 0.2876(4) 0.0387(8) Uani 1 d . .
H16A H 1.6840(62) 1.2023(83) 0.3556(60) 0.079(19) Uiso 1 d . .
H16B H 1.5889(61) 1.2786(133) 0.2226(61) 0.104(21) Uiso 1 d . .
H16C H 1.6456(60) 1.1237(90) 0.2504(57) 0.078(19) Uiso 1 d . .
C17 C 1.5745(3) 1.1697(4) 0.5386(3) 0.0303(7) Uani 1 d . .
H17A H 1.5281(41) 1.2274(49) 0.5848(36) 0.035(11) Uiso 1 d . .
H17B H 1.6395(41) 1.2288(48) 0.5324(35) 0.031(10) Uiso 1 d . .
C18 C 1.6399(4) 1.0249(5) 0.6116(3) 0.0294(8) Uani 1 d . .
H18 H 1.5786(34) 0.9496(44) 0.6078(30) 0.010(8) Uiso 1 d . .
C19 C 1.7405(4) 0.9561(5) 0.5698(4) 0.0387(8) Uani 1 d . .
H19A H 1.7072(44) 0.9265(62) 0.4887(45) 0.040(11) Uiso 1 d . .
H19B H 1.7881(50) 0.8631(70) 0.6163(45) 0.055(13) Uiso 1 d . .
H19C H 1.8052(42) 1.0429(54) 0.5799(38) 0.030(10) Uiso 1 d . .
O4 O 1.7074(2) 1.0625(4) 0.7440(2) 0.0344(6) Uani 1 d . .
O5 O 1.5207(3) 1.0660(4) 0.7729(2) 0.0471(7) Uani 1 d . .
C20 C 1.6375(4) 1.0688(5) 0.8142(3) 0.0366(8) Uani 1 d . .
C21 C 1.7224(5) 1.0773(7) 0.9509(4) 0.0518(11) Uani 1 d . .
H21A H 1.7574(62) 0.9837(90) 0.9687(57) 0.077(19) Uiso 1 d . .
H21B H 1.6603(53) 1.1216(68) 0.9977(49) 0.056(14) Uiso 1 d . .
H21C H 1.7900(66) 1.1543(89) 0.9579(58) 0.078(20) Uiso 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
Br 0.0246(2) 0.0553(3) 0.0508(2) 0.0031(2) 0.00853(12) -0.0034(2)
C1 0.0242(14) 0.038(2) 0.040(2) -0.001(2) 0.0091(13) 0.0025(15)
C2 0.029(2) 0.046(2) 0.041(2) 0.001(2) 0.0183(15) 0.004(2)
C3 0.030(2) 0.045(2) 0.031(2) -0.002(2) 0.0138(13) 0.003(2)
C4 0.0262(14) 0.031(2) 0.0272(14) -0.0021(14) 0.0096(12) 0.0060(14)
C5 0.0241(14) 0.027(2) 0.0276(14) 0.0028(13) 0.0068(11) 0.0057(13)
C6 0.0274(15) 0.038(2) 0.030(2) 0.0011(15) 0.0067(12) 0.0024(14)
N 0.0277(13) 0.034(2) 0.0230(12) -0.0041(12) 0.0075(10) 0.0005(12)
C7 0.0258(14) 0.024(2) 0.0264(14) 0.0002(13) 0.0045(12) 0.0029(13)
C8 0.028(2) 0.032(2) 0.0231(15) 0.0028(14) 0.0029(12) -0.0006(14)
C9 0.033(2) 0.033(2) 0.0267(15) 0.0024(14) 0.0114(12) -0.002(2)
C10 0.030(2) 0.029(2) 0.0300(15) 0.0027(14) 0.0096(12) -0.0007(14)
C11 0.0240(15) 0.025(2) 0.0254(14) 0.0001(12) 0.0044(12) -0.0016(13)
C12 0.027(2) 0.025(2) 0.0237(14) 0.0002(13) 0.0041(12) 0.0016(14)
O1 0.0282(11) 0.0390(14) 0.0246(10) 0.0001(10) 0.0019(9) -0.0032(11)
O2 0.059(2) 0.055(2) 0.047(2) 0.0029(15) 0.0045(14) 0.021(2)
C13 0.028(2) 0.054(3) 0.0266(15) 0.006(2) 0.0072(12) 0.003(2)
C14 0.038(2) 0.074(3) 0.028(2) 0.005(2) -0.003(2) -0.016(2)
O3 0.0484(15) 0.056(2) 0.0275(11) 0.0029(12) 0.0154(10) -0.0099(14)
C15 0.054(3) 0.077(3) 0.044(2) -0.012(2) 0.031(2) -0.004(3)
C16 0.035(2) 0.048(2) 0.032(2) -0.001(2) 0.0125(15) -0.012(2)
C17 0.0278(15) 0.031(2) 0.0275(14) -0.0052(14) 0.0049(12) -0.0052(15)
C18 0.026(2) 0.033(2) 0.026(2) -0.0020(14) 0.0060(13) -0.004(2)
C19 0.032(2) 0.044(2) 0.037(2) -0.002(2) 0.0097(14) 0.004(2)
O4 0.0270(12) 0.045(2) 0.0238(11) 0.0003(11) 0.0020(10) -0.0025(11)
O5 0.0357(13) 0.069(2) 0.0351(12) -0.0004(14) 0.0126(10) -0.0041(14)
C20 0.040(2) 0.039(2) 0.028(2) -0.001(2) 0.0098(14) -0.004(2)
C21 0.057(3) 0.061(3) 0.029(2) 0.001(2) 0.008(2) 0.001(3)

_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
Br C1 1.906(3) . ?
C1 C6 1.381(5) . ?
C1 C2 1.403(5) . ?
C2 C3 1.382(5) . ?
C2 H2 0.94(4) . ?
C3 C4 1.396(5) . ?
C3 H3 1.02(4) . ?
C4 N 1.379(4) . ?
C4 C5 1.418(4) . ?
C5 C6 1.400(5) . ?
C5 C7 1.439(5) . ?
C6 H6 0.94(5) . ?
N C12 1.388(5) . ?
N H1 0.92(5) . ?
C7 C8 1.378(5) . ?
C7 C12 1.414(5) . ?
C8 C9 1.395(5) . ?
C8 O1 1.405(4) . ?
C9 O3 1.379(4) . ?
C9 C10 1.406(5) . ?
C10 C11 1.401(4) . ?
C10 C16 1.507(5) . ?
C11 C12 1.396(5) . ?
C11 C17 1.525(4) . ?
O1 C13 1.359(5) . ?
O2 C13 1.189(6) . ?
C13 C14 1.492(5) . ?
C14 H14A 0.97(7) . ?
C14 H14B 0.95(8) . ?
C14 H14C 0.91(6) . ?
O3 C15 1.431(6) . ?
C15 H15A 1.08(9) . ?
C15 H15B 0.87(7) . ?
C15 H15C 1.02(6) . ?
C16 H16A 0.89(7) . ?
C16 H16B 1.00(10) . ?
C16 H16C 0.91(7) . ?
C17 C18 1.520(5) . ?
C17 H17A 1.01(4) . ?
C17 H17B 0.91(4) . ?
C18 O4 1.459(4) . ?
C18 C19 1.506(5) . ?
C18 H18 0.93(4) . ?
C19 H19A 0.90(5) . ?
C19 H19B 0.99(6) . ?
C19 H19C 1.01(5) . ?
O4 C20 1.327(4) . ?
O5 C20 1.211(5) . ?
C20 C21 1.502(5) . ?
C21 H21A 0.88(7) . ?
C21 H21B 1.10(6) . ?
C21 H21C 0.98(7) . ?

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
C6 C1 C2 122.7(3) . . ?
C6 C1 Br 119.3(3) . . ?
C2 C1 Br 118.0(3) . . ?
C3 C2 C1 120.3(3) . . ?
C3 C2 H2 116.8(22) . . ?
C1 C2 H2 122.8(22) . . ?
C2 C3 C4 118.0(3) . . ?
C2 C3 H3 121.3(27) . . ?
C4 C3 H3 120.6(27) . . ?
N C4 C3 129.4(3) . . ?
N C4 C5 109.1(3) . . ?
C3 C4 C5 121.6(3) . . ?
C6 C5 C4 119.9(3) . . ?
C6 C5 C7 134.0(3) . . ?
C4 C5 C7 106.1(3) . . ?
C1 C6 C5 117.5(3) . . ?
C1 C6 H6 117.9(28) . . ?
C5 C6 H6 124.5(28) . . ?
C4 N C12 109.2(3) . . ?
C4 N H1 124.0(33) . . ?
C12 N H1 126.8(33) . . ?
C8 C7 C12 117.6(3) . . ?
C8 C7 C5 135.0(3) . . ?
C12 C7 C5 107.4(3) . . ?
C7 C8 C9 120.6(3) . . ?
C7 C8 O1 120.5(3) . . ?
C9 C8 O1 118.7(3) . . ?
O3 C9 C8 119.3(3) . . ?
O3 C9 C10 119.6(3) . . ?
C8 C9 C10 121.0(3) . . ?
C11 C10 C9 119.8(3) . . ?
C11 C10 C16 122.7(3) . . ?
C9 C10 C16 117.4(3) . . ?
C12 C11 C10 117.4(3) . . ?
C12 C11 C17 117.8(3) . . ?
C10 C11 C17 124.7(3) . . ?
N C12 C11 128.3(3) . . ?
N C12 C7 108.2(3) . . ?
C11 C12 C7 123.5(3) . . ?
C13 O1 C8 117.3(3) . . ?
O2 C13 O1 122.7(3) . . ?
O2 C13 C14 127.1(4) . . ?
O1 C13 C14 110.2(4) . . ?
C13 C14 H14A 105.3(44) . . ?
C13 C14 H14B 102.4(44) . . ?
H14A C14 H14B 98.6(63) . . ?
C13 C14 H14C 96.6(33) . . ?
H14A C14 H14C 131.5(64) . . ?
H14B C14 H14C 118.3(54) . . ?
C9 O3 C15 114.4(3) . . ?
O3 C15 H15A 112.6(45) . . ?
O3 C15 H15B 108.5(44) . . ?
H15A C15 H15B 108.1(64) . . ?
O3 C15 H15C 112.5(38) . . ?
H15A C15 H15C 114.7(53) . . ?
H15B C15 H15C 99.2(48) . . ?
C10 C16 H16A 120.9(40) . . ?
C10 C16 H16B 109.4(38) . . ?
H16A C16 H16B 118.7(62) . . ?
C10 C16 H16C 112.1(43) . . ?
H16A C16 H16C 93.1(53) . . ?
H16B C16 H16C 98.6(54) . . ?
C18 C17 C11 110.9(3) . . ?
C18 C17 H17A 110.0(23) . . ?
C11 C17 H17A 106.4(24) . . ?
C18 C17 H17B 105.3(25) . . ?
C11 C17 H17B 113.1(24) . . ?
H17A C17 H17B 111.2(34) . . ?
O4 C18 C19 105.7(3) . . ?
O4 C18 C17 110.5(3) . . ?
C19 C18 C17 113.7(3) . . ?
O4 C18 H18 106.2(20) . . ?
C19 C18 H18 110.3(21) . . ?
C17 C18 H18 110.2(21) . . ?
C18 C19 H19A 112.3(30) . . ?
C18 C19 H19B 116.9(29) . . ?
H19A C19 H19B 105.1(45) . . ?
C18 C19 H19C 105.6(24) . . ?
H19A C19 H19C 108.6(38) . . ?
H19B C19 H19C 108.1(37) . . ?
C20 O4 C18 117.3(3) . . ?
O5 C20 O4 124.2(3) . . ?
O5 C20 C21 124.8(4) . . ?
O4 C20 C21 111.1(3) . . ?
C20 C21 H21A 104.4(41) . . ?
C20 C21 H21B 105.5(28) . . ?
H21A C21 H21B 120.6(51) . . ?
C20 C21 H21C 106.1(37) . . ?
H21A C21 H21C 109.1(57) . . ?
H21B C21 H21C 110.1(48) . . ?

_refine_diff_density_max         .406
_refine_diff_density_min         -.606
_refine_diff_density_rms         .053