Asymmetric Rh(I)-Catalyzed Intramolecular [3 + 2] Cycloaddition of 1-Yne-vinylcyclopropanes for Bicyclo[3.3.0] Compounds with a Chiral Quaternary Carbon Stereocenter and Density Functional Theory Study of the Origins of Enantioselectivity
Mu Lin; Guan-Yu Kang; Yi-An Guo; Zhi-Xiang Yu; Journal of the American Chemical Society 134 (2012) 398–405; doi:10.1021/ja2082119

data_4117235
_publ_section_title
;
 Asymmetric Rh(I)-Catalyzed Intramolecular [3 + 2] Cycloaddition of
 1-Yne-vinylcyclopropanes for Bicyclo[3.3.0] Compounds with a Chiral
 Quaternary Carbon Stereocenter and Density Functional Theory Study of the
 Origins of Enantioselectivity
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              398
_journal_page_last               405
_journal_paper_doi               10.1021/ja2082119
_journal_volume                  134
_journal_year                    2012
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C16 H19 N O2 S'
_chemical_formula_sum            'C16 H19 N O2 S'
_chemical_formula_weight         289.38
_space_group_IT_number           5
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'C 2y'
_symmetry_space_group_name_H-M   'C 1 2 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                 106.99(3)
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   16.901(3)
_cell_length_b                   9.2889(19)
_cell_length_c                   19.688(4)
_cell_measurement_reflns_used    5167
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      27.4833
_cell_measurement_theta_min      1.0815
_cell_volume                     2956.0(11)
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2008)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2008)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2008)'
_computing_molecular_graphics
;
 Mercury: visualization and analysis of crystal structures, C. F. Macrae,
 P. R. Edgington, P. McCabe, E. Pidcock, G. P. Shields, R. Taylor,
 M. Towler and J. van de Streek, J. Appl. Cryst., 39, 453-457, 2006.
;
_computing_publication_material  'SHELX-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      173(2)
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Saturn724+ CCD'
_diffrn_measurement_method       '\w scans at fixed \c = 45\%'
_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  0.0431
_diffrn_reflns_av_sigmaI/netI    0.0409
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_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            20508
_diffrn_reflns_theta_full        27.48
_diffrn_reflns_theta_max         27.48
_diffrn_reflns_theta_min         1.08
_exptl_absorpt_coefficient_mu    0.220
_exptl_absorpt_correction_T_max  0.9475
_exptl_absorpt_correction_T_min  0.9054
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2008)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.301
_exptl_crystal_description       block
_exptl_crystal_F_000             1232
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.34
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.445
_refine_diff_density_min         -0.258
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.04(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     361
_refine_ls_number_reflns         6742
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0568
_refine_ls_R_factor_gt           0.0531
_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^)+(0.0590P)^2^+2.0085P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1308
_refine_ls_wR_factor_ref         0.1336
_reflns_number_gt                6321
_reflns_number_total             6742
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja2082119_si_001.cif
_cod_data_source_block           a
_cod_original_cell_volume        2955.9(10)
_cod_database_code               4117235