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_4122946
_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_absolute_configuration unk
_chemical_formula_moiety         'C23 H23 N3 O2'
_chemical_formula_sum            'C23 H23 N3 O2'
_chemical_formula_weight         373.44
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-07-11
_audit_creation_method
;
Olex2 1.2
(compiled 2014.06.27 svn.r2953 for OlexSys, GUI svn.r4855)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.206(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.0926(7)
_cell_length_b                   10.6133(8)
_cell_length_c                   9.8276(8)
_cell_measurement_reflns_used    6614
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      30.53
_cell_measurement_theta_min      2.25
_cell_volume                     942.83(13)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (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 0.997
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker Kappa Apex2 Duo'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'focusing graphite'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0178
_diffrn_reflns_av_unetI/netI     0.0190
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            11450
_diffrn_reflns_point_group_measured_fraction_full 0.753
_diffrn_reflns_point_group_measured_fraction_max 0.675
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.557
_diffrn_reflns_theta_min         2.084
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.085
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6995
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0340 before and 0.0311 after correction.
The Ratio of minimum to maximum transmission is 0.9375.
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    1.315
_exptl_crystal_description       prism
_exptl_crystal_F_000             396
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.471
_refine_diff_density_min         -0.198
_refine_diff_density_rms         0.048
_refine_ls_abs_structure_details
;
 Flack x determined using 836 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.1(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     261
_refine_ls_number_reflns         3893
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0356
_refine_ls_R_factor_gt           0.0341
_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^)+(0.0563P)^2^+0.1980P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0898
_refine_ls_wR_factor_ref         0.0911
_reflns_Friedel_coverage         0.291
_reflns_Friedel_fraction_full    0.475
_reflns_Friedel_fraction_max     0.320
_reflns_number_gt                3732
_reflns_number_total             3893
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja509893s_si_003.cif
_cod_data_source_block           mo_ca090714_0m
_cod_database_code               4122946
_shelxl_version_number           2014-3
_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
 N2-H2 = N3-H3
 0.91 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C6(H6), C14(H14)
3.b Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B)
3.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2A), C3(H3A), C9(H9), C11(H11), C16(H16), C17(H17), C18(H18),
 C19(H19)
3.d X=CH2 refined with riding coordinates:
 C10(H10A,H10B)
3.e Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C)
;
_olex2_submission_original_sample_id ca090714
_olex2_submission_special_instructions 'No special instructions were received'