An efficient synthesis strategy to the core structure of 6-5-6-5-6-membered epipolythiodiketopiperazines.
Zipfel, Hannes F.; Carreira, Erick M.; Organic letters 16 (2014) 2854–2857; doi:10.1021/ol500990f

data_1516149
_publ_section_title
;
 An efficient synthesis strategy to the core structure of
 6-5-6-5-6-membered epipolythiodiketopiperazines.
;
_journal_issue                   11
_journal_name_full               'Organic letters'
_journal_page_first              2854
_journal_page_last               2857
_journal_paper_doi               10.1021/ol500990f
_journal_volume                  16
_journal_year                    2014
_chemical_absolute_configuration syn
_chemical_formula_moiety         '0.5(C H2 Cl2), C32 H30 N2 O6'
_chemical_formula_sum            'C32.5 H31 Cl N2 O6'
_chemical_formula_weight         581.04
_chemical_name_systematic
(2R,4aS,7aR,9R,11aS,14aR)-7a,14a-bis(benzyloxy)-2,9-dihydroxy-1,7a,8,9,11a,14a-hexahydropyrazino[1,2-a:4,5-a']diindole-6,13(2H,4aH)-dione
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      5
_symmetry_space_group_name_Hall  'C 2y'
_symmetry_space_group_name_H-M   'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2013-09-04
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.976(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   43.265(2)
_cell_length_b                   15.0547(7)
_cell_length_c                   10.2366(4)
_cell_measurement_reflns_used    7869
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      66.07
_cell_measurement_theta_min      4.33
_cell_volume                     6651.5(5)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.945
_diffrn_measured_fraction_theta_max 0.944
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker Kappa Apex2 Duo'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'double mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0481
_diffrn_reflns_av_unetI/netI     0.0686
_diffrn_reflns_Laue_measured_fraction_full 0.945
_diffrn_reflns_Laue_measured_fraction_max 0.944
_diffrn_reflns_limit_h_max       51
_diffrn_reflns_limit_h_min       -50
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            19920
_diffrn_reflns_point_group_measured_fraction_full 0.727
_diffrn_reflns_point_group_measured_fraction_max 0.726
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         67.78
_diffrn_reflns_theta_min         4.33
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.365
_exptl_absorpt_correction_T_max  0.8983
_exptl_absorpt_correction_T_min  0.6700
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1002 before and 0.0706 after correction.
The Ratio of minimum to maximum transmission is 0.7459.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.160
_exptl_crystal_description       needle
_exptl_crystal_F_000             2440
_exptl_crystal_recrystallization_method 'Crystallized from CH2Cl2'
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.015
_refine_diff_density_max         0.524
_refine_diff_density_min         -0.662
_refine_diff_density_rms         0.090
_refine_ls_abs_structure_details
;
 Flack x determined using 1934 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.15(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     709
_refine_ls_number_reflns         8767
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0869
_refine_ls_R_factor_gt           0.0773
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.1579P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2051
_refine_ls_wR_factor_ref         0.2159
_reflns_Friedel_coverage         0.478
_reflns_Friedel_fraction_full    0.491
_reflns_Friedel_fraction_max     0.490
_reflns_number_gt                7143
_reflns_number_total             8767
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol500990f_si_004.cif
_cod_data_source_block           cu_ca250813_0m
_cod_depositor_comments
;
Adding full bibliography for 1516147--1516149.cif.

2019-08-17
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_sg_symbol_H-M      'C 2'
_cod_original_formula_moiety     'C H2 Cl2, 2(C32 H30 N2 O6)'
_cod_original_formula_sum        'C65 H62 Cl2 N4 O12'
_cod_original_formula_units_Z    4
_cod_original_formula_weight     1162.08
_cod_database_code               1516149
_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 O(H) groups
2. Uiso/Uaniso restraints and constraints
Uiso(C26B) = Uiso(C26A)
Uiso(C32B) = Uiso(C32A)
Uiso(C31B) = Uiso(C31A)
Uiso(C30B) = Uiso(C30A)
Uiso(C29A) = Uiso(C29B)
Uiso(C28A) = Uiso(C28B)
Uiso(C27B) = Uiso(C27A)
Uiso(O6A) = Uiso(O6B)
3. Others
 Sof(O6B)=Sof(C26B)=Sof(H26C)=Sof(H26D)=Sof(C27B)=Sof(C32B)=Sof(H32B)=
 Sof(C31B)=Sof(H31B)=Sof(C30B)=Sof(H30B)=Sof(C29B)=Sof(H29B)=Sof(C28B)=
 Sof(H28B)=1-FVAR(1)
 Sof(O6A)=Sof(C26A)=Sof(H26A)=Sof(H26B)=Sof(C32A)=Sof(H31A)=Sof(C27A)=
 Sof(C28A)=Sof(H27A)=Sof(C29A)=Sof(H28A)=Sof(C30A)=Sof(H29A)=Sof(C31A)=
 Sof(H30A)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C7(H7), C10(H10), C12(H12), C16(H16), C7'(H7'), C10'(H10'), C12'(H12'),
 C16'(H16')
4.b Secondary CH2 refined with riding coordinates:
 C33(H33A,H33B), C11(H11C,H11D), C15(H15C,H15D), C19(H19C,H19D), C26(H26E,
 H26F), C11'(H11A,H11B), C15'(H15A,H15B), C19'(H19A,H19B), C26A(H26A,H26B),
 C26B(H26C,H26D)
4.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C8(H8), C13(H13), C14(H14), C17(H17), C18(H18), C21(H21), C22(H22),
 C23(H23), C24(H24), C25(H25), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32),
  C5'(H5'), C8'(H8'), C13'(H13'), C14'(H14'), C17'(H17'), C18'(H18'),
 C21'(H21'), C22'(H22'), C23'(H23'), C24'(H24'), C25'(H25'), C32B(H32B),
 C31B(H31B), C30B(H30B), C29B(H29B), C28B(H28B), C32A(H31A), C28A(H27A),
 C29A(H28A), C30A(H29A), C31A(H30A)
4.d Fitted hexagon refined as free rotating group:
 C27B(C32B,C31B,C30B,C29B,C28B), C32A(C27A,C28A,C29A,C30A,C31A)
4.e Tetrahedral OH refined with riding coordinates:
 O3(H3), O4(H4), O3'(H3'), O4'(H4')
;
_shelx_hkl_checksum              61987
_shelx_res_checksum              53558
_shelxl_version_number           2012-9