ZnI2-Catalyzed Diastereoselective [4 + 2] Cycloadditions of β,γ-Unsaturated α-Ketothioesters with Olefins.
Mal, Kanchan; Das, Supriya; Maiti, Nakul C.; Natarajan, Ramalingam; Das, Indrajit; The Journal of organic chemistry 80 (2015) 2972–2988; doi:10.1021/jo5024766

data_4030783
_publ_section_title
;
 ZnI2-Catalyzed Diastereoselective [4 + 2] Cycloadditions of
 \b,\g-Unsaturated \a-Ketothioesters with Olefins.
;
_journal_issue                   6
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              2972
_journal_page_last               2988
_journal_paper_doi               10.1021/jo5024766
_journal_volume                  80
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H21 Br O3 S'
_chemical_formula_sum            'C21 H21 Br O3 S'
_chemical_formula_weight         433.35
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_symmetry_space_group_name_Hall  'P 2c -2n'
_symmetry_space_group_name_H-M   'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-08-14
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   25.0058(12)
_cell_length_b                   13.0551(6)
_cell_length_c                   12.6318(5)
_cell_measurement_reflns_used    4618
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      19.250
_cell_measurement_theta_min      2.773
_cell_volume                     4123.7(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0891
_diffrn_reflns_av_unetI/netI     0.1413
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            36259
_diffrn_reflns_point_group_measured_fraction_full 0.940
_diffrn_reflns_point_group_measured_fraction_max 0.891
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.602
_diffrn_reflns_theta_min         1.760
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.112
_exptl_absorpt_correction_T_max  0.7411
_exptl_absorpt_correction_T_min  0.5928
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/3 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.0998 before and 0.0841 after correction.
The Ratio of minimum to maximum transmission is 0.7999.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_density_diffrn    1.396
_exptl_crystal_description       needle
_exptl_crystal_F_000             1776
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.201
_refine_diff_density_min         -0.219
_refine_diff_density_rms         0.048
_refine_ls_abs_structure_details
;
 Flack x determined using 1259 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.013(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.934
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     473
_refine_ls_number_reflns         8536
_refine_ls_number_restraints     49
_refine_ls_restrained_S_all      0.932
_refine_ls_R_factor_all          0.1661
_refine_ls_R_factor_gt           0.0452
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0051P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0652
_refine_ls_wR_factor_ref         0.0867
_reflns_Friedel_coverage         0.741
_reflns_Friedel_fraction_full    0.874
_reflns_Friedel_fraction_max     0.794
_reflns_number_gt                3783
_reflns_number_total             8536
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo5024766_si_006.cif
_cod_data_source_block           km340-2_a
_cod_depositor_comments
'Adding full bibliography for 4030777--4030784.cif.'
_cod_database_code               4030783
_shelxl_version_number           2014/6
_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. Rigid bond restraints
 C33, C34, C35, C36, C37, C38
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
4.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C21(H21), C22(H22), C23(H23), C24(H24)
4.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C32(H32A,H32B)
4.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C014(H014), C14(H14), C15(H15), C16(H16),
 C17(H17), C27(H27), C28(H28), C29(H29), C30(H30), C34(H34), C35(H35), C36(H36),
  C37(H37), C38(H38)
4.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C40(H40A,H40B,H40C), C41(H41A,H41B,
 H41C)
;
_shelx_res_checksum              63793
_shelx_hkl_checksum              34273
_olex2_submission_special_instructions 'No special instructions were received'