Diastereoselective Rhodium-Catalyzed Ene-Cycloisomerization Reactions of Alkenylidenecyclopropanes: Total Synthesis of (-)-α-Kainic Acid
P. Andrew Evans; Phillip A. Inglesby; Journal of the American Chemical Society 134 (2012) 3635–3638; doi:10.1021/ja210804r

data_4117557
_publ_section_title
;
 Diastereoselective Rhodium-Catalyzed Ene-Cycloisomerization Reactions of
 Alkenylidenecyclopropanes: Total Synthesis of (-)-\a-Kainic Acid
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3635
_journal_page_last               3638
_journal_paper_doi               10.1021/ja210804r
_journal_volume                  134
_journal_year                    2012
_chemical_formula_moiety         'C23 H27 N5 O6 S, 2(C H2 Cl2)'
_chemical_formula_sum            'C25 H31 Cl4 N5 O6 S'
_chemical_formula_weight         671.41
_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                74.910(4)
_cell_angle_beta                 82.690(4)
_cell_angle_gamma                83.941(4)
_cell_formula_units_Z            2
_cell_length_a                   10.744(3)
_cell_length_b                   11.488(3)
_cell_length_c                   12.803(3)
_cell_measurement_reflns_used    4914
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.10
_cell_measurement_theta_min      0.90
_cell_volume                     1509.0(7)
_computing_cell_refinement       'SAINT v6.45a (Bruker, 2005)'
_computing_data_collection       'SMART v.5.632 (Bruker, 2005)'
_computing_data_reduction        'SAINT v6.45a (Bruker, 2005)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.974
_diffrn_measured_fraction_theta_max 0.974
_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  0.0185
_diffrn_reflns_av_sigmaI/netI    0.0337
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            7954
_diffrn_reflns_theta_full        25.68
_diffrn_reflns_theta_max         25.68
_diffrn_reflns_theta_min         2.40
_exptl_absorpt_coefficient_mu    0.509
_exptl_absorpt_correction_T_max  0.9508
_exptl_absorpt_correction_T_min  0.8222
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS V2008-1 (Bruker, 2008)'
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.475
_exptl_crystal_description       prism
_exptl_crystal_F_000             694
_exptl_crystal_size_max          0.40
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.10
_refine_diff_density_max         1.735
_refine_diff_density_min         -0.986
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     377
_refine_ls_number_reflns         5571
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0729
_refine_ls_R_factor_gt           0.0626
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0808P)^2^+3.9173P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1581
_refine_ls_wR_factor_ref         0.1671
_reflns_number_gt                4750
_reflns_number_total             5571
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja210804r_si_002.cif
_cod_data_source_block           pI-IV-71m
_cod_database_code               4117557