Iron(II)-Catalyzed Asymmetric Intramolecular Aminohydroxylation of Indoles.
Zhang, Yong-Qiang; Yuan, Yong-An; Liu, Guan-Sai; Xu, Hao; Organic letters 15 (2013) 3910–3913; doi:10.1021/ol401666e

data_1512200
_publ_section_title
;
 Iron(II)-Catalyzed Asymmetric Intramolecular Aminohydroxylation of
 Indoles.
;
_journal_issue                   15
_journal_name_full               'Organic letters'
_journal_page_first              3910
_journal_page_last               3913
_journal_paper_doi               10.1021/ol401666e
_journal_volume                  15
_journal_year                    2013
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C32 H25 Cl2 N3 O7 S, C H Cl3'
_chemical_formula_sum            'C33 H26 Cl5 N3 O7 S'
_chemical_formula_weight         785.88
_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     iterative
_audit_creation_date             2013-04-04
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.6220(13)
_cell_length_b                   18.082(2)
_cell_length_c                   19.975(3)
_cell_measurement_reflns_used    9090
_cell_measurement_temperature    172.3
_cell_measurement_theta_max      29.77
_cell_measurement_theta_min      2.25
_cell_volume                     3475.4(8)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_collection       'APEX2 v2011.2-4 (Bruker, 2011)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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      172.3
_diffrn_detector_area_resol_mean 512
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.953
_diffrn_measurement_device_type  'Bruker D8 diffractometer with APEX2 detector'
_diffrn_measurement_method       '\f and \w scans with a narrow frame width'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0350
_diffrn_reflns_av_unetI/netI     0.0451
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            30478
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.934
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.892
_diffrn_reflns_theta_min         2.039
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.530
_exptl_absorpt_correction_T_max  0.7463
_exptl_absorpt_correction_T_min  0.5784
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1090 before and 0.0502 after correction.
The Ratio of minimum to maximum transmission is 0.7750.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.502
_exptl_crystal_description       'rect. Prism'
_exptl_crystal_F_000             1608
_exptl_crystal_size_max          0.928
_exptl_crystal_size_mid          0.331
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.653
_refine_diff_density_min         -0.528
_refine_diff_density_rms         0.077
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   -0.01(7)
_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     476
_refine_ls_number_reflns         11170
_refine_ls_number_restraints     158
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0706
_refine_ls_R_factor_gt           0.0561
_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^)+(0.0836P)^2^+0.7511P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1352
_refine_ls_wR_factor_ref         0.1451
_reflns_Friedel_coverage         0.777
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.910
_reflns_number_gt                9253
_reflns_number_total             11170
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol401666e_si_003.cif
_cod_data_source_block           trypt
_cod_database_code               1512200
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
2. Restrained distances
 C27A-C26A \\sim C28A-C27A \\sim C29A-C28A \\sim C30A-C29A \\sim C31A-C30A \\sim C31A-C26A
 with sigma of 0.005
 N3B-C22 \\sim N3A-C22
 with sigma of 0.02
 N3A-C22 \\sim N3B-C22
 with sigma of 0.02
 N3A-C22 \\sim N3B-C22
 with sigma of 0.002
3. Uiso/Uaniso restraints and constraints
Uanis(C25A) = Uanis(C25B)
Uanis(O7A) = Uanis(O7B)
Uanis(C26A) = Uanis(C26B)
Uanis(C27A) = Uanis(C27B)
Uanis(C31A) = Uanis(C31B)
Uanis(C29A) = Uanis(C29B)
Uanis(C28A) = Uanis(C28B)
Uanis(C30A) = Uanis(C30B)
Uanis(O6A) = Uanis(O6B)
Uanis(C24A) = Uanis(C24B)
Uanis(N3A) = Uanis(N3B)
4. Same fragment restrains
{N3B, C24B, O6B, O7B, C25B, C26B, C27B, C28B, C29B, C30B, C31B}
as
{N3A, C24A, O6A, O7A, C25A, C26A, C27A, C28A, C29A, C30A, C31A}
5. Others
 1-Sof(H3B)=1-Sof(H3B)=1-Sof(H3B)=1-Sof(H3B)=1-Sof(H3B)=1-Sof(H3B)=1-Sof(H3B)=
 1-Sof(H3B)=1-Sof(H3B)=1-Sof(H3B)=1-Sof(H3B)=1-Sof(H3B)=1-Sof(H3B)=1-Sof(H3B)=1-
 Sof(H3B)=1-Sof(H3B)=1-Sof(H3B)=1-Sof(H3B)=1-Sof(H3B)=Sof(N3A)=Sof(H3A)=
 Sof(C24A)=Sof(O6A)=Sof(O7A)=Sof(C25A)=Sof(H25C)=Sof(H25D)=Sof(C26A)=Sof(C27A)=
 Sof(H27A)=Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(H30A)=
 Sof(C31A)=Sof(H31A)=1-Sof(H3B)=Sof(H22)
6.a Ternary CH refined with riding coordinates:
 C7(H7), C22(H22A), C22(H22), C1L(H1L)
6.b Secondary CH2 refined with riding coordinates:
 C25B(H25A,H25B), C25A(H25C,H25D), C21(H21A,H21B)
6.c Aromatic/amide H refined with riding coordinates:
 N3B(H3B), C27B(H27B), C28B(H28B), C29B(H29B), C30B(H30B), C31B(H31B),
 N3A(H3A), C27A(H27A), C28A(H28A), C29A(H29A), C30A(H30A), C31A(H31A), N2(H2),
 C12(H12), C10(H10), C11(H11), C9(H9), C1(H1), C2(H2A), C19(H19), C15(H15),
 C16(H16), C5(H5), C17(H17), C18(H18)
;
_shelxl_version_number           2012-9