Ir-Catalyzed Reverse Prenylation of 3-Substituted Indoles: Total Synthesis of (+)-Aszonalenin and (-)-Brevicompanine B.
Ruchti, Jonathan; Carreira, Erick M.; Journal of the American Chemical Society  (2014) 141119074653005–; doi:10.1021/ja509893s

data_4122947
_publ_section_title
;
 Ir-Catalyzed Reverse Prenylation of 3-Substituted Indoles: Total
 Synthesis of (+)-Aszonalenin and (-)-Brevicompanine B.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              141119074653005
_journal_paper_doi               10.1021/ja509893s
_journal_year                    2014
_chemical_formula_moiety         'C22 H26 N2 O2 S'
_chemical_formula_sum            'C22 H26 N2 O2 S'
_chemical_formula_weight         382.51
_chemical_name_systematic
3a-(2-methylbut-3-en-2-yl)-1-tosyl-1,2,3,3a,8,8a-hexahydropyrrolo[2,3-b]indole
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-02-25
_audit_creation_method
;
Olex2 1.2
(compiled 2014.02.11 svn.r2872 for OlexSys, GUI svn.r4767)
;
_cell_angle_alpha                90
_cell_angle_beta                 121.932(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.5108(6)
_cell_length_b                   10.3083(4)
_cell_length_c                   16.0724(7)
_cell_measurement_reflns_used    8589
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      27.53
_cell_measurement_theta_min      2.48
_cell_volume                     1899.73(15)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    OLEX2
_computing_publication_material  OLEX2
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'XS (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 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker/Nonius Kappa Apex2'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0391
_diffrn_reflns_av_unetI/netI     0.0310
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            32625
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.602
_diffrn_reflns_theta_min         2.477
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.191
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6977
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0519 before and 0.0493 after correction.
The Ratio of minimum to maximum transmission is 0.9358.
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    1.337
_exptl_crystal_description       prism
_exptl_crystal_F_000             816
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.380
_refine_diff_density_min         -0.423
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     250
_refine_ls_number_reflns         4397
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0510
_refine_ls_R_factor_gt           0.0372
_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^)+(0.0363P)^2^+1.2487P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0856
_refine_ls_wR_factor_ref         0.0933
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3562
_reflns_number_total             4397
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja509893s_si_002.cif
_cod_data_source_block           ca240214_0m
_cod_database_code               4122947
_shelxl_version_number           2013-4
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-H1
 0.91 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C4(H4)
3.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C17(H17A,H17B)
3.c Aromatic/amide H refined with riding coordinates:
 C1(H1A), C2(H2), C6(H6), C7(H7), C11(H11), C14(H14), C15(H15), C19(H19),
 C20(H20)
3.d X=CH2 refined with riding coordinates:
 C10(H10A,H10B)
3.e Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C)
;
_olex2_computing_structure_refinement_long 'SHELXL-97 (Sheldrick, 2008)'
_olex2_computing_structure_solution_long 'SHELXS-97 (Sheldrick, 2008)'