On the Mechanism of an Asymmetric α,β-Unsaturated Carboxylic Acid Hydrogenation: Application to the Synthesis of a PGD2 Receptor Antagonist
David M. Tellers; J. Christopher McWilliams; Guy Humphrey; Michel Journet; Lisa DiMichele; Joseph Hinksmon; Arlene E. McKeown; Thorsten Rosner; Yongkui Sun; Richard D. Tillyer; Journal of the American Chemical Society 128 (2006) 17063–17073; doi:10.1021/ja0623358

data_4111245
_publ_contact_author_address
; Process Research 
 Merck Research Laboratories 
 P.O. Box 2000 
 Rahway, NJ 07065 
 USA 
;
_publ_contact_author_email       david_tellers@merck.com
_publ_contact_author_name        'David M. Tellers'
_publ_section_title
;
 On the Mechanism of an Asymmetric \a,\b-Unsaturated Carboxylic Acid
 Hydrogenation: Application to the Synthesis of a PGD2 Receptor Antagonist
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              17063
_journal_page_last               17073
_journal_paper_doi               10.1021/ja0623358
_journal_volume                  128
_journal_year                    2006
_chemical_formula_moiety         'C21 H17 Cl F N O4 S'
_chemical_formula_sum            'C21 H17 Cl F N O4 S'
_chemical_formula_weight         433.87
_chemical_name_common            'Compound 1-endo'
_chemical_name_systematic
'  [benzyl-7-fluoro-5-(mthylsulfnyl)-1,4-dihydrocyclpent[b]indol-3-yl]oac'
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 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                 98.5310(10)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   11.0378(8)
_cell_length_b                   10.2260(7)
_cell_length_c                   17.1981(12)
_cell_measurement_reflns_used    5560
_cell_measurement_temperature    223(2)
_cell_measurement_theta_max      26.40
_cell_measurement_theta_min      2.32
_cell_volume                     1919.7(2)
_computing_cell_refinement       'Bruker SMART'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      223(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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  0.0543
_diffrn_reflns_av_sigmaI/netI    0.0445
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            20053
_diffrn_reflns_theta_full        26.43
_diffrn_reflns_theta_max         26.43
_diffrn_reflns_theta_min         1.87
_exptl_absorpt_coefficient_mu    0.347
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.501
_exptl_crystal_description       Tetrahedron
_exptl_crystal_F_000             896
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.360
_refine_diff_density_min         -0.353
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     264
_refine_ls_number_reflns         3942
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0671
_refine_ls_R_factor_gt           0.0488
_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^)+(0.0497P)^2^+0.9402P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1058
_refine_ls_wR_factor_ref         0.1133
_reflns_number_gt                3087
_reflns_number_total             3942
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja0623358si20060420_020531.cif
_cod_data_source_block           endo
_cod_database_code               4111245