An asymmetric approach to bicyclo[2.2.1]heptane-1-carboxylates via a formal [4 + 2] cycloaddition reaction enabled by organocatalysis.
Fu, Jian-Guo; Shan, Yi-Fan; Sun, Wang-Bin; Lin, Guo-Qiang; Sun, Bing-Feng; Organic & biomolecular chemistry 14 (2016) 5229–5232; doi:10.1039/c6ob00814c

data_7155124
_publ_section_title
;
 An asymmetric approach to bicyclo[2.2.1]heptane-1-carboxylates via a
 formal [4 + 2] cycloaddition reaction enabled by organocatalysis.
;
_journal_issue                   23
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              5229
_journal_page_last               5232
_journal_paper_doi               10.1039/c6ob00814c
_journal_volume                  14
_journal_year                    2016
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C17 H21 N O5 S'
_chemical_formula_sum            'C17 H21 N O5 S'
_chemical_formula_weight         351.41
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-03-25
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2016-04-16 deposited with the CCDC.
2016-05-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.5608(8)
_cell_length_b                   13.1579(14)
_cell_length_c                   16.9471(18)
_cell_measurement_reflns_used    5211
_cell_measurement_temperature    130
_cell_measurement_theta_max      29.24
_cell_measurement_theta_min      2.40
_cell_volume                     1686.0(3)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      130
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0316
_diffrn_reflns_av_unetI/netI     0.0341
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            17174
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.553
_diffrn_reflns_theta_min         1.959
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.219
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6962
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0867 before and 0.0454 after correction.
The Ratio of minimum to maximum transmission is 0.9331.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.384
_exptl_crystal_description       block
_exptl_crystal_F_000             744
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.335
_refine_diff_density_min         -0.267
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details
;
 Flack x determined using 1842 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.08(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     219
_refine_ls_number_reflns         5177
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0462
_refine_ls_R_factor_gt           0.0395
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0509P)^2^+0.2587P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0933
_refine_ls_wR_factor_ref         0.0970
_reflns_Friedel_coverage         0.763
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                4640
_reflns_number_total             5177
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6ob00814c2.cif
_cod_data_source_block           mo_dm15213_0m
_cod_depositor_comments          'Adding full bibliography for 7155124.cif.'
_cod_database_code               7155124
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.968
_shelx_estimated_absorpt_t_min   0.947
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{S1, C15'}
{S1', C15}
3. Uiso/Uaniso restraints and constraints
S1' \\sim C16 \\sim C17 \\sim S1: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C16) \\sim Ueq, Uanis(C17) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(S1) = Uanis(C15')
Uanis(S1') = Uanis(C15)
4. Others
 Fixed Sof: S1(0.5) C15(0.5) H15(0.5) S1'(0.5) C15'(0.5) H15'(0.5) H16(0.5)
 H16A(0.5) H17(0.5) H17A(0.5)
5.a Ternary CH refined with riding coordinates:
 C4(H4), C5(H5)
5.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C7(H7A,H7B), C10(H10A,H10B), C12(H12A,H12B), C13(H13A,H13B)
5.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C15'(H15'), C16(H16), C16(H16A), C17(H17), C17(H17A)
5.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C11(H11A,H11B,H11C)
;
_shelx_res_checksum              20931
_olex2_submission_special_instructions 'No special instructions were received'