# 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
'Karl Anker Jorgensen'
'Stephan Bachmann'
'Soren Bertelsen'
'Alan Braunton'
'Nis Halland'
'Mauro Marigo'

_publ_contact_author_name        'Karl Anker Jorgensen'
_publ_contact_author_address     
;
Department of Chemistry
Aarhus University
Center for Metal Catalyzed Reaction
Aarhus C
DK-8000
DENMARK
;

_publ_contact_author_email       KAJ@CHEM.AU.DK

_publ_requested_journal          'Chemical Communications'

_publ_section_title              
;
Organocatalytic Asymmetric a-Bromination of Aldehydes
and Ketones
;

_publ_section_references         
;

Altomare,A., Cascarano,G., Giacovazzo,C., Guagliardi,A.,
Moliterni,.A,G,G., Burla,M.C., Polidori,G., Camalli,M.
& Spagna,R. (1997). SIR97. University of Bari, Italy.

Bruker (2003. SAINT. Version 7.06a. Bruker AXS Inc., Madison,
Wisconsin, U.S.A.

Bruker-Nonius (2003). APEX2. Version 1.0-6. Bruker-Nonius BV,
Delft, Thw Netherlands.

Burnett,M.N. & Johnson,C.K. (1996). ORTEP-III. Report ORNL-6895.
Oak Ridge National Laboratory, Tennessee, USA.

Busing,W.R., Martin,K.O. & Levy,H.A. (1962). ORFLS. Report
ORNL-TM-305. Oak Ridge National Laboratory, Tennessee, USA.

Hazell,A. (1995). KRYSTAL, An integrated system of
crystallographic programs. Aarhus University, Denmark.

Rogers,D. (1981). Acta Cryst. A37, 734-741.

Sheldrick,G.M. (2003) SADABS. Version 2.10. Bruker AXS Inc.,
Madison, Wisconsin, USA.

;
#==============================================================================

data_nh1890s
_database_code_depnum_ccdc_archive 'CCDC 277076'

#====================================

# 5. CHEMICAL DATA

_chemical_name_systematic        
;
3-bromotetrahydropyran-4-one
;
_chemical_formula_sum            'C5 H7 Br O2'
_chemical_formula_moiety         'C5 H7 Br O2'
_chemical_formula_weight         179.01
_chemical_melting_point          ?
_chemical_compound_source        ?

#====================================
# 6. CRYSTAL DATA

_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'

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

_cell_length_a                   4.3135(4)
_cell_length_b                   11.327(1)
_cell_length_c                   12.558(1)
_cell_angle_alpha                90.000
_cell_angle_beta                 90.000
_cell_angle_gamma                90.000
_cell_volume                     613.57(9)
_cell_formula_units_Z            4
_cell_measurement_temperature    100
_cell_measurement_reflns_used    5654
_cell_measurement_theta_min      3.60
_cell_measurement_theta_max      34.60
_exptl_crystal_description       needle
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.52
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_exptl_crystal_density_meas      'not measured'
_exptl_crystal_density_diffrn    1.938
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             352
_exptl_absorpt_coefficient_mu    6.602
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS, 2003 '
_exptl_absorpt_correction_T_min  0.453
_exptl_absorpt_correction_T_max  0.718

#====================================

# 7. EXPERIMENTAL DATA

_diffrn_ambient_temperature      100
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_source         'x-ray tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device       
;
Bruker-Nonius X8Apex-II CCD diffractometer
;
_diffrn_measurement_method       
;
Thin-slice \w and \f scans
;
_diffrn_standards_decay_%        0
_diffrn_reflns_number            15870
_diffrn_reflns_av_R_equivalents  0.053
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_theta_min         3.60
_diffrn_reflns_theta_max         34.60
_diffrn_reflns_reduction_process 15870
_reflns_number_total             2615
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measured_fraction_theta_full 0.996
_diffrn_reflns_theta_full        34.60
_reflns_number_gt                2585
_reflns_threshold_expression     'I> 0.0 '
_computing_data_collection       'Apex2 (Bruker-Nonius, 2003 )'
_computing_cell_refinement       'SAINT (Bruker, 2003)'
_computing_data_reduction        'SAINT (Bruker, 2003)'
_computing_structure_solution    
;
SIR97 (Altomare et al., 1997 ) , KRYSTAL
;
_computing_structure_refinement  'modified ORFLS(1962), KRYSTAL'
_computing_molecular_graphics    
;
ORTEP-III (Burnett & Johnson, 1996), KRYSTAL
;
_computing_publication_material  KRYSTAL
_atom_type_scat_source           IntTabIV

#====================================

# 8. REFINEMENT DATA

_refine_ls_structure_factor_coef F
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
w= 1/{[\s~cs~(F^2^)+B+(1+A)F^2^]^1/2^^- |F|}^2^
where A = 0.0300 and B = 0.50
;
_refine_ls_hydrogen_treatment    refall
_refine_ls_extinction_method     
;
Type 1 Lorentzian isotropic ( Becker and Coppens, 1974)
;
_refine_ls_extinction_coef       17(5)
_refine_ls_abs_structure_details 
; A factor according to Rogers (1981) was included in the least squares
refinement using all positive reflections, including 1063 Bijvoet pairs.
;
_refine_ls_abs_structure_Rogers  1.00(2)
_refine_ls_number_reflns         2585
_refine_ls_number_parameters     103
_refine_ls_number_restraints     0
_refine_ls_number_constraints    0
_refine_ls_R_factor_gt           0.031
_refine_ls_wR_factor_ref         0.033
_refine_ls_goodness_of_fit_ref   0.870
_refine_ls_shift/su_max          0.0007
_refine_ls_shift/su_mean         0.0001
_refine_diff_density_max         1.3(2)
_refine_diff_density_min         -1.0(2)

#==========================================

# 9. ATOMIC COORDINATES AND THERMAL PARAMETERS

loop_
_atom_site_label
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_thermal_displace_type
Br1 0.16152(5) 0.63981(2) 0.05857(2) 0.01771(9) Uij
O1 0.6455(5) 0.3271(1) 0.0865(1) 0.0231(7) Uij
O2 0.0242(4) 0.5090(2) 0.2659(1) 0.0200(7) Uij
C2 0.4683(6) 0.4193(2) 0.0390(2) 0.0201(9) Uij
C3 0.3956(4) 0.5124(2) 0.1232(2) 0.0150(8) Uij
C4 0.2327(5) 0.4602(2) 0.2197(2) 0.0156(8) Uij
C5 0.3712(6) 0.3441(2) 0.2556(2) 0.0202(9) Uij
C6 0.4593(7) 0.2644(2) 0.1623(2) 0.0241(10) Uij
H2a 0.592(7) 0.449(3) -0.020(2) 0.016(7) Uiso
H2b 0.286(6) 0.386(2) 0.012(2) 0.004(6) Uiso
H3 0.578(6) 0.546(2) 0.146(2) 0.001(5) Uiso
H5a 0.555(8) 0.354(3) 0.289(3) 0.025(8) Uiso
H5b 0.206(9) 0.296(3) 0.308(3) 0.030(9) Uiso
H6a 0.272(9) 0.237(3) 0.136(3) 0.032(9) Uiso
H6b 0.594(10) 0.202(4) 0.179(3) 0.044(11) Uiso

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_12
_atom_site_aniso_U_13
_atom_site_aniso_U_23
Br1 0.01601(9) 0.01560(9) 0.02151(10) 0.00150(8) 0.00080(8) 0.00403(8)
O1 0.0263(8) 0.0201(7) 0.0228(7) 0.0090(7) 0.0054(7) 0.0004(6)
O2 0.0162(7) 0.0259(8) 0.0179(7) 0.0007(6) 0.0033(6) -0.0009(6)
C2 0.0236(10) 0.0193(9) 0.0174(10) 0.0053(8) 0.0029(7) -0.0012(7)
C3 0.0130(8) 0.0153(8) 0.0166(8) 0.0001(6) -0.0008(6) -0.0001(7)
C4 0.0137(8) 0.0181(9) 0.0151(8) -0.0030(6) -0.0016(6) -0.0028(7)
C5 0.0220(10) 0.0189(9) 0.0198(9) 0.0009(8) 0.0024(8) 0.0044(7)
C6 0.0306(11) 0.0167(9) 0.0248(10) 0.0033(9) 0.0028(9) 0.0018(8)

#=================================

# 10. MOLECULAR GEOMETRY

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
Br1 C3 1.940(2)
O1 C2 1.425(3)
O1 C6 1.434(3)
O2 C4 1.205(3)
C2 C3 1.526(3)
C3 C4 1.520(3)
C4 C5 1.513(3)
C5 C6 1.527(3)
C2 H2b 0.932(27)
C2 H2a 0.973(31)
C3 H3 0.923(24)
C5 H5a 0.907(35)
C5 H5b 1.115(36)
C6 H6a 0.929(38)
C6 H6b 0.934(41)

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
C6 O1 C2 109.9(2)
C3 C2 O1 109.1(2)
C2 C3 C4 112.2(2)
Br1 C3 C4 112.5(1)
Br1 C3 C2 109.3(1)
C5 C4 O2 123.3(2)
C3 C4 O2 123.4(2)
C3 C4 C5 113.1(2)
C6 C5 C4 112.6(2)
C5 C6 O1 110.8(2)
H2a C2 H2b 109.1(23)
O1 C2 H2b 108.0(15)
C3 C2 H2b 110.8(16)
O1 C2 H2a 106.1(18)
C3 C2 H2a 113.4(18)
C4 C3 H3 107.8(15)
C2 C3 H3 109.3(15)
Br1 C3 H3 105.3(15)
H5b C5 H5a 110.3(28)
C4 C5 H5a 112.0(21)
C6 C5 H5a 102.4(21)
C4 C5 H5b 110.4(18)
C6 C5 H5b 109.0(18)
H6b C6 H6a 111.7(33)
O1 C6 H6a 114.4(22)
C5 C6 H6a 104.9(22)
O1 C6 H6b 99.9(25)
C5 C6 H6b 115.3(26)