Highly Enantioselective Reductive Cyclization of Acetylenic Aldehydes via Rhodium Catalyzed Asymmetric Hydrogenation
Jong Uk Rhee; Michael J. Krische; Journal of the American Chemical Society 128 (2006) 10674–10675; doi:10.1021/ja0637954

data_4110828
_publ_section_title
;
 Highly Enantioselective Reductive Cyclization of Acetylenic Aldehydes via
 Rhodium Catalyzed Asymmetric Hydrogenation
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10674
_journal_page_last               10675
_journal_paper_doi               10.1021/ja0637954
_journal_volume                  128
_journal_year                    2006
_chemical_formula_sum            'C21 H22 Br N O4 S'
_chemical_formula_weight         464.37
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_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                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   5.9234(1)
_cell_length_b                   16.2878(3)
_cell_length_c                   21.0361(4)
_cell_measurement_reflns_used    2612
_cell_measurement_temperature    153(2)
_cell_measurement_theta_max      27.5
_cell_measurement_theta_min      1
_cell_volume                     2029.55(6)
_computing_cell_refinement       'Collect software, Nonius B.V. 1998'
_computing_data_collection       'Collect software, Nonius B.V. 1998'
_computing_data_reduction
;
DENZO and Scalepack (Otwinoski and Minor, 1997)
;
_computing_molecular_graphics    'XP SHELXTL/PC, Siemens Analytical'
_computing_structure_refinement  'XL SHELXTL/PC, Siemens Analytical'
_computing_structure_solution
;

SIR97 - Altomare A., Burla M.C., Camalli M., Cascarano G.L., Giacovazzo C., 
Guagliardi A., Moliterni A.G.G., Polidori G.,Spagna R.
;
_diffrn_ambient_temperature      153(2)
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Nonius Kappa CCD'
_diffrn_measurement_method       \w-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  0.0534
_diffrn_reflns_av_sigmaI/netI    0.0537
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            18234
_diffrn_reflns_theta_full        27.47
_diffrn_reflns_theta_max         27.47
_diffrn_reflns_theta_min         2.30
_exptl_absorpt_coefficient_mu    2.156
_exptl_absorpt_correction_T_max  0.871
_exptl_absorpt_correction_T_min  0.673
_exptl_absorpt_correction_type   gaussian
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.520
_exptl_crystal_description       needles
_exptl_crystal_F_000             952
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.075
_exptl_crystal_size_min          0.075
_refine_diff_density_max         0.359
_refine_diff_density_min         -0.418
_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   0.301(7)
_refine_ls_extinction_coef       0.0013(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     310
_refine_ls_number_reflns         4623
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0539
_refine_ls_R_factor_gt           0.0344
_refine_ls_shift/su_max          0.029
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0212P)^2^+0.7430P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0611
_refine_ls_wR_factor_ref         0.0673
_reflns_number_gt                3742
_reflns_number_total             4623
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja0637954rom20060530_054753.cif
_cod_data_source_block           tosylbr
_cod_database_code               4110828