Enantioselective Rhodium-Catalyzed [2 + 2 + 2] Cycloadditions of Terminal Alkynes and Alkenyl Isocyanates: Mechanistic Insights Lead to a Unified Model that Rationalizes Product Selectivity
Derek M. Dalton; Kevin M. Oberg; Robert T. Yu; Ernest E. Lee; Stéphane Perreault; Mark Emil Oinen; Melissa L. Pease; Guillaume Malik; Tomislav Rovis; Journal of the American Chemical Society 131 (2009) 15717–15728; doi:10.1021/ja905065j

data_4105233
_publ_section_title
;
 Enantioselective Rhodium-Catalyzed [2 + 2 + 2] Cycloadditions of Terminal
 Alkynes and Alkenyl Isocyanates: Mechanistic Insights Lead to a Unified
 Model that Rationalizes Product Selectivity
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              15717
_journal_page_last               15728
_journal_paper_doi               10.1021/ja905065j
_journal_volume                  131
_journal_year                    2009
_chemical_absolute_configuration ad
_chemical_formula_sum            'C45 H52 Cl5 N O4 P Rh'
_chemical_formula_weight         982.01
_chemical_name_systematic
;

 ?

;
_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           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 91.835(3)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   10.8926(7)
_cell_length_b                   18.1189(11)
_cell_length_c                   11.2230(7)
_cell_measurement_reflns_used    9470
_cell_measurement_temperature    120
_cell_measurement_theta_max      36.48
_cell_measurement_theta_min      2.89
_cell_volume                     2213.9(2)
_computing_cell_refinement       'APEX2 (Bruker, 2009)'
_computing_data_collection       'APEX2 (Bruker, 2009)'
_computing_data_reduction        'APEX2 (Bruker, 2009)'
_computing_molecular_graphics    'APEX2 (Bruker, 2009)'
_computing_publication_material  'APEX2 (Bruker, 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      120
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  '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  0.0257
_diffrn_reflns_av_sigmaI/netI    0.0267
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            77157
_diffrn_reflns_theta_full        35.63
_diffrn_reflns_theta_max         35.63
_diffrn_reflns_theta_min         2.14
_exptl_absorpt_coefficient_mu    0.767
_exptl_absorpt_correction_T_max  0.8249
_exptl_absorpt_correction_T_min  0.7898
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Sheldrick, G. M. (2008)'
_exptl_crystal_colour            gold
_exptl_crystal_density_diffrn    1.473
_exptl_crystal_description       cubic
_exptl_crystal_F_000             1012
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.30
_exptl_crystal_size_min          0.26
_refine_diff_density_max         1.092
_refine_diff_density_min         -0.978
_refine_diff_density_rms         0.061
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.016(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     517
_refine_ls_number_reflns         20295
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0246
_refine_ls_R_factor_gt           0.0232
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0310P)^2^+0.4016P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0574
_refine_ls_wR_factor_ref         0.0581
_reflns_number_gt                19606
_reflns_number_total             20295
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja905065j_si_006.cif
_cod_data_source_block           rovis81
_cod_database_code               4105233