Tandem Rh(I)-Catalyzed [(5+2)+1] Cycloaddition/Aldol Reaction for the Construction of Linear Triquinane Skeleton: Total Syntheses of (\±)-Hirsutene and (\±)-1-Desoxyhypnophilin
Lei Jiao; Changxia Yuan; Zhi-Xiang Yu; Journal of the American Chemical Society 130 (2008) 4421–4430; doi:10.1021/ja7100449

data_4107616
_publ_contact_author_address
;Peking University
Beijing, 100871
P. R. China
;
_publ_contact_author_email       yuzx@pku.edu.cn
_publ_contact_author_fax         86-10-62751708
_publ_contact_author_name        'Zhi-Xiang Yu'
_publ_contact_author_phone       86-10-62752612
_publ_section_title
;
 Tandem Rh(I)-Catalyzed [(5+2)+1] Cycloaddition/Aldol Reaction for the
 Construction of Linear Triquinane Skeleton: Total Syntheses of
 (\+-)-Hirsutene and (\+-)-1-Desoxyhypnophilin
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4421
_journal_page_last               4430
_journal_paper_doi               10.1021/ja7100449
_journal_volume                  130
_journal_year                    2008
_chemical_compound_source        'organic synthesis'
_chemical_formula_moiety         'C19 H25 N O4 S'
_chemical_formula_sum            'C19 H25 N O4 S'
_chemical_formula_weight         363.46
_chemical_melting_point          428
_chemical_name_common            '6-5-5 product'
_chemical_name_systematic
N-tosyl-5-aza-9-hydroxy-1-methyltricyclo[7.3.0.02,7]dodecan-12-one
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_Int_Tables_number      2
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                83.29(3)
_cell_angle_beta                 84.99(3)
_cell_angle_gamma                70.12(3)
_cell_formula_units_Z            2
_cell_length_a                   6.3978(13)
_cell_length_b                   8.4177(17)
_cell_length_c                   17.485(4)
_cell_measurement_reflns_used    12874
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      27.48
_cell_measurement_theta_min      2.17
_cell_volume                     878.3(4)
_computing_cell_refinement       'Rapid Auto(Rigaku 2001)'
_computing_data_collection       'Rapid Auto(Rigaku 2001)'
_computing_data_reduction        'Rapid Auto(Rigaku 2001)'
_computing_molecular_graphics    'XP in Siemens SHELXTL (Sheldrick, 1994)'
_computing_publication_material  'SHELX97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1997)'
_diffrn_ambient_pressure         100
_diffrn_ambient_temperature      173(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Rigaku raxis Rapid IP Area Detector'
_diffrn_measurement_method       '\w scans at fixed \c = 45\%'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0230
_diffrn_reflns_av_sigmaI/netI    0.0333
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            5583
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         25.00
_diffrn_reflns_theta_min         1.17
_diffrn_source                   'rotating anode'
_exptl_absorpt_coefficient_mu    0.209
_exptl_absorpt_correction_T_max  0.9835
_exptl_absorpt_correction_T_min  0.9459
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'ABSCOR by T.Higashi    8 March, 1995'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.374
_exptl_crystal_description       plate
_exptl_crystal_F_000             388
_exptl_crystal_recrystallization_method 'from PE and EtOAc'
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.387
_refine_diff_density_min         -0.315
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.124
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     226
_refine_ls_number_reflns         3098
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.124
_refine_ls_R_factor_all          0.0633
_refine_ls_R_factor_gt           0.0505
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0528P)^2^+0.6463P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1164
_refine_ls_wR_factor_ref         0.1221
_reflns_number_gt                2702
_reflns_number_total             3098
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja7100449-file005.cif
_cod_data_source_block           2296
_cod_original_cell_volume        878.3(3)
_cod_database_code               4107616