Mechanistic Studies and Expansion of the Substrate Scope of Direct Enantioselective Alkynylation of α-Ketiminoesters Catalyzed by Adaptable (Phebox)Rhodium(III) Complexes.
Morisaki, Kazuhiro; Sawa, Masanao; Yonesaki, Ryohei; Morimoto, Hiroyuki; Mashima, Kazushi; Ohshima, Takashi; Journal of the American Chemical Society 138 (2016) 6194–6203; doi:10.1021/jacs.6b01590

data_4125070
_publ_section_title
;
 Mechanistic Studies and Expansion of the Substrate Scope of Direct
 Enantioselective Alkynylation of \a-Ketiminoesters Catalyzed by Adaptable
 (Phebox)Rhodium(III) Complexes.
;
_journal_issue                   19
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6194
_journal_page_last               6203
_journal_paper_doi               10.1021/jacs.6b01590
_journal_volume                  138
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_sum            'C34 H27 N2 O4 Rh'
_chemical_formula_weight         630.49
_chemical_name_systematic
; 
 ? 
;
_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                   10.7300(14)
_cell_length_b                   14.3916(19)
_cell_length_c                   18.130(2)
_cell_measurement_reflns_used    9934
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      28.31
_cell_measurement_theta_min      2.21
_cell_volume                     2799.7(6)
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      296(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.939
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_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  0.0220
_diffrn_reflns_av_sigmaI/netI    0.0260
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            15770
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         28.40
_diffrn_reflns_theta_min         1.81
_exptl_absorpt_coefficient_mu    0.653
_exptl_crystal_density_diffrn    1.496
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             1288
_refine_diff_density_max         0.711
_refine_diff_density_min         -0.372
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.010(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     371
_refine_ls_number_reflns         6352
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0178
_refine_ls_R_factor_gt           0.0175
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0203P)^2^+0.7331P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0451
_refine_ls_wR_factor_ref         0.0453
_reflns_number_gt                6276
_reflns_number_total             6352
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja6b01590_si_002.cif
_cod_data_source_block           rhphpheboxccphoac_0m1
_cod_depositor_comments
'Adding full bibliography for 4125069--4125071.cif.'
_cod_original_sg_symbol_H-M      P212121
_cod_database_code               4125070