Oxidative Furan-to-Indole Rearrangement. Synthesis of 2-(2-Acylvinyl)indoles and Flinderole C Analogues.
Makarov, Anton S.; Merkushev, Anton A.; Uchuskin, Maxim G.; Trushkov, Igor V.; Organic letters 18 (2016) 2192–2195; doi:10.1021/acs.orglett.6b00805

data_1555547
_publ_section_title
;
 Oxidative Furan-to-Indole Rearrangement. Synthesis of
 2-(2-Acylvinyl)indoles and Flinderole C Analogues.
;
_journal_issue                   9
_journal_name_full               'Organic letters'
_journal_page_first              2192
_journal_page_last               2195
_journal_paper_doi               10.1021/acs.orglett.6b00805
_journal_volume                  18
_journal_year                    2016
_chemical_formula_moiety         'C38 H34 N2, C2 H6 O S'
_chemical_formula_sum            'C40 H40 N2 O S'
_chemical_formula_weight         596.80
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2015-12-30
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                78.265(9)
_cell_angle_beta                 69.761(11)
_cell_angle_gamma                81.577(9)
_cell_formula_units_Z            2
_cell_length_a                   10.2707(13)
_cell_length_b                   12.5581(13)
_cell_length_c                   14.2615(15)
_cell_measurement_reflns_used    4033
_cell_measurement_temperature    295(2)
_cell_measurement_theta_max      28.0050
_cell_measurement_theta_min      3.0550
_cell_volume                     1684.0(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      295.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4752
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.842
_diffrn_measurement_details
;
  1 omega   -7.00   74.00   1.0000   45.0000
omega____ theta____ kappa____ phi______ frames
    -       13.8509   38.0000  -30.0000 81

  2 omega  -12.00   19.00   1.0000   45.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.3978  -99.0000  -60.0000 31

  3 omega  -62.00   43.00   1.0000   45.0000
omega____ theta____ kappa____ phi______ frames
    -       13.8509  -38.0000  150.0000 105

  4 omega  -82.00   14.00   1.0000   45.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.3978  -57.0000   30.0000 96
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Xcalibur, Ruby'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0080175000
_diffrn_orient_matrix_UB_12      -0.0574395000
_diffrn_orient_matrix_UB_13      0.0022638000
_diffrn_orient_matrix_UB_21      0.0696060000
_diffrn_orient_matrix_UB_22      -0.0008651000
_diffrn_orient_matrix_UB_23      -0.0008537000
_diffrn_orient_matrix_UB_31      -0.0233650000
_diffrn_orient_matrix_UB_32      -0.0071262000
_diffrn_orient_matrix_UB_33      0.0536863000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0330
_diffrn_reflns_av_unetI/netI     0.0468
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.842
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            13384
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.842
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.281
_diffrn_reflns_theta_min         2.989
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.129
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72189
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.177
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             636
_exptl_crystal_size_max          0.54
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.159
_refine_diff_density_min         -0.346
_refine_diff_density_rms         0.037
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     445
_refine_ls_number_reflns         7745
_refine_ls_number_restraints     84
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0769
_refine_ls_R_factor_gt           0.0539
_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^)+(0.0629P)^2^+0.2487P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1287
_refine_ls_wR_factor_ref         0.1486
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5518
_reflns_number_total             7745
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol6b00805_si_003.cif
_cod_data_source_block           psu-301(mu-2)
_cod_original_cell_volume        1684.0(3)
_cod_database_code               1555547
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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
 C1SA, C1SB, S1SB, S1SA, O1SB, O1SA, C2SB, C2SA
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C2SB \\sim S1SB \\sim O1SA \\sim O1SB \\sim S1SA \\sim C1SB \\sim C1SA \\sim
C2SA: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
4. Same fragment restrains
{S1SA, O1SA, C1SA, C2SA} sigma for 1-2: 0.02, 1-3: 0.04
as
{S1SB, O1SB, C1SB, C2SB}
5. Others
 Sof(S1SB)=Sof(O1SB)=Sof(C1SB)=Sof(H1SD)=Sof(H1SE)=Sof(H1SF)=Sof(C2SB)=
 Sof(H2SD)=Sof(H2SE)=Sof(H2SF)=1-FVAR(1)
 Sof(S1SA)=Sof(O1SA)=Sof(C1SA)=Sof(H1SA)=Sof(H1SB)=Sof(H1SC)=Sof(C2SA)=
 Sof(H2SA)=Sof(H2SB)=Sof(H2SC)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C19(H19)
6.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B)
6.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C10(H10), C11(H11), C12(H12), C13(H13),
 C14(H14), C15(H15), C16(H16), C23(H23), C24(H24), C25(H25), C26(H26), C29(H29),
  C30(H30), C31(H31), C32(H32), C33(H33), C34(H34)
6.d Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C1SA(H1SA,H1SB,
 H1SC), C2SA(H2SA,H2SB,H2SC), C1SB(H1SD,H1SE,H1SF), C2SB(H2SD,H2SE,H2SF)
;
_shelx_res_checksum              81551
_shelx_hkl_checksum              1770
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'