Rhodium-Catalyzed Enantioselective Cyclizations of γ-Alkynylaldehydes with Acyl Phosphonates: Ligand- and Substituent-Controlled C-P or C-H Bond Cleavage
Kengo Masuda; Norifumi Sakiyama; Rie Tanaka; Keiichi Noguchi; Ken Tanaka; Journal of the American Chemical Society 133 (2011) 6918–6921; doi:10.1021/ja201337x

data_4106121
_publ_contact_author_address
;
Department of Applied Chemistry
Graduate School of Engineering
Tokyo University of Agriculture and Technology
Koganei
Tokyo 184-8588
Japan
;
_publ_contact_author_email       tanaka-k@cc.tuat.ac.jp
_publ_contact_author_fax         +81-42-388-7037
_publ_contact_author_name        'Dr Ken Tanaka'
_publ_contact_author_phone       +81-42-388-7037
_publ_section_title
;
 Rhodium-Catalyzed Enantioselective Cyclizations of \g-Alkynylaldehydes
 with Acyl Phosphonates: Ligand- and Substituent-Controlled C-P or C-H
 Bond Cleavage
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6918
_journal_page_last               6921
_journal_paper_doi               10.1021/ja201337x
_journal_volume                  133
_journal_year                    2011
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H28 N O7 P S'
_chemical_formula_sum            'C23 H28 N O7 P S'
_chemical_formula_weight         493.49
_chemical_name_systematic
;
 (S)-Benzoic acid
 4-(diethoxyphosphorylmethylene)-1-
 (toluene-4-sulfonyl)pyrrolidin-3-yl ester
;
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      19
_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_date             2010-12-01
_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                   8.5255(2)
_cell_length_b                   10.0064(2)
_cell_length_c                   28.4762(5)
_cell_measurement_reflns_used    40505
_cell_measurement_temperature    193(2)
_cell_measurement_theta_max      68.27
_cell_measurement_theta_min      3.11
_cell_volume                     2429.29(9)
_computing_cell_refinement       'RAPID AUTO'
_computing_data_collection       'RAPID AUTO (Rigaku, 2009)'
_computing_data_reduction        'RAPID AUTO'
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'Il Milione (Burla, et al., 2007)'
_diffrn_ambient_temperature      193(2)
_diffrn_detector_area_resol_mean 10.000
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Rigaku R-AXIS RAPID'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'rotating anode'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54187
_diffrn_reflns_av_R_equivalents  0.0345
_diffrn_reflns_av_sigmaI/netI    0.0226
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            45260
_diffrn_reflns_theta_full        68.19
_diffrn_reflns_theta_max         68.19
_diffrn_reflns_theta_min         3.10
_exptl_absorpt_coefficient_mu    2.181
_exptl_absorpt_correction_T_max  0.916
_exptl_absorpt_correction_T_min  0.442
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   'NUMABS (Rigaku, 1999)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.349
_exptl_crystal_description       platelet
_exptl_crystal_F_000             1040
_exptl_crystal_size_max          0.60
_exptl_crystal_size_mid          0.30
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.226
_refine_diff_density_min         -0.323
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
'Flack H D (1983), Acta Cryst. A39, 876-881.  1873 Friedel Pairs'
_refine_ls_abs_structure_Flack   0.020(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.993
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     318
_refine_ls_number_reflns         4421
_refine_ls_number_restraints     60
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0442
_refine_ls_R_factor_gt           0.0393
_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^)+(0.0803P)^2^+0.2722P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1066
_refine_ls_wR_factor_ref         0.1127
_reflns_number_gt                3872
_reflns_number_total             4421
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja201337x_si_001.cif
_cod_data_source_block           I
_cod_database_code               4106121