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_4030780
_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           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             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            4
_cell_length_a                   11.1799(15)
_cell_length_b                   11.3455(14)
_cell_length_c                   14.897(2)
_cell_measurement_reflns_used    8988
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      27.23
_cell_measurement_theta_min      2.56
_cell_volume                     1889.6(4)
_computing_cell_refinement       'SAINT v7.34A (Bruker, 200?)'
_computing_data_reduction        'SAINT v7.34A (Bruker, 200?)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.978
_diffrn_measured_fraction_theta_max 0.972
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0445
_diffrn_reflns_av_unetI/netI     0.0465
_diffrn_reflns_Laue_measured_fraction_full 0.978
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            12659
_diffrn_reflns_point_group_measured_fraction_full 0.944
_diffrn_reflns_point_group_measured_fraction_max 0.931
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.284
_diffrn_reflns_theta_min         2.278
_exptl_absorpt_coefficient_mu    2.304
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.554422
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2004/1 (Bruker,2004) was used for absorption correction.
R(int) was 0.2209 before and 0.0764 after correction.
The Ratio of minimum to maximum transmission is 0.5544.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_density_diffrn    1.523
_exptl_crystal_description       block
_exptl_crystal_F_000             888
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.26
_refine_diff_density_max         0.353
_refine_diff_density_min         -0.520
_refine_diff_density_rms         0.091
_refine_ls_abs_structure_details
;
 Flack x determined using 1347 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.066(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.175
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     237
_refine_ls_number_reflns         3955
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.175
_refine_ls_R_factor_all          0.0367
_refine_ls_R_factor_gt           0.0286
_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^)+(0.0166P)^2^+0.7408P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0626
_refine_ls_wR_factor_ref         0.0785
_reflns_Friedel_coverage         0.684
_reflns_Friedel_fraction_full    0.898
_reflns_Friedel_fraction_max     0.876
_reflns_number_gt                3573
_reflns_number_total             3955
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo5024766_si_004.cif
_cod_data_source_block           id_km337_jul14_0m
_cod_depositor_comments
'Adding full bibliography for 4030777--4030784.cif.'
_cod_database_code               4030780
_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.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B)
2.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12), C14(H14), C15(H15), C16(H16), C17(H17),
 C18(H18)
2.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C)
;
_shelx_res_checksum              9290
_shelx_hkl_checksum              17282
_olex2_submission_special_instructions 'No special instructions were received'