Enantioselective Rhodium-Catalyzed [2+2+2] Cycloaddition of Alkenyl Isocyanates and Terminal Alkynes: Application to the Total Synthesis of (+)-Lasubine II
Robert T. Yu; Tomislav Rovis; Journal of the American Chemical Society 128 (2006) 12370–12371; doi:10.1021/ja064868m

data_4110927
_publ_section_title
;
 Enantioselective Rhodium-Catalyzed [2+2+2] Cycloaddition of Alkenyl
 Isocyanates and Terminal Alkynes: Application to the Total Synthesis of
 (+)-Lasubine II
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              12370
_journal_page_last               12371
_journal_paper_doi               10.1021/ja064868m
_journal_volume                  128
_journal_year                    2006
_chemical_absolute_configuration ad
_chemical_formula_sum            'C14 H14 Br N O'
_chemical_formula_weight         292.17
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           'Bruker SHELXTL'
_cell_angle_alpha                90.00
_cell_angle_beta                 100.668(4)
_cell_angle_gamma                90.00
_cell_formula_units_Z            6
_cell_length_a                   12.5864(8)
_cell_length_b                   8.6454(6)
_cell_length_c                   17.4451(12)
_cell_measurement_reflns_used    7806
_cell_measurement_temperature    100
_cell_measurement_theta_max      31.25
_cell_measurement_theta_min      2.38
_cell_volume                     1865.5(2)
_computing_cell_refinement       'Bruker SMART'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_structure_solution    'Bruker SHELXTL'
_diffrn_ambient_temperature      373(2)
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker Apex2 CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0498
_diffrn_reflns_av_sigmaI/netI    0.0605
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            55388
_diffrn_reflns_theta_full        31.53
_diffrn_reflns_theta_max         31.53
_diffrn_reflns_theta_min         1.65
_exptl_absorpt_coefficient_mu    3.288
_exptl_absorpt_correction_T_max  0.7541
_exptl_absorpt_correction_T_min  0.6783
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS, Sheldrick, 1997'
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.560
_exptl_crystal_description       cube
_exptl_crystal_F_000             888
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.583
_refine_diff_density_min         -0.511
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.006(5)
_refine_ls_goodness_of_fit_ref   0.744
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     461
_refine_ls_number_reflns         12412
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.744
_refine_ls_R_factor_all          0.0482
_refine_ls_R_factor_gt           0.0327
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0737P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0806
_refine_ls_wR_factor_ref         0.0895
_reflns_number_gt                10226
_reflns_number_total             12412
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja064868msi20060708_041012.cif
_cod_data_source_block           rovis23a
_cod_database_code               4110927