Experimental Evidence for the All-Up Reactive Conformation of Chiral Rhodium(II) Carboxylate Catalysts: Enantioselective Synthesis of cis-Cyclopropane α-Amino Acids
Vincent N. G. Lindsay; Wei Lin; André B. Charette; Journal of the American Chemical Society 131 (2009) 16383–16385; doi:10.1021/ja9044955

data_4105352
_publ_contact_author_address
;
      Universit\'e de Montr\'eal
      D\'epartement de Chimie
      C.P. 6128, Succ. Centre-ville
      Montr\'eal, Qu\'ebec
      Canada, H3C 3J7
;
_publ_contact_author_email       andre.charette@umontreal.ca
_publ_contact_author_fax         '+1 514 343 5900'
_publ_contact_author_name        'Dr Andr\'e B. Charette'
_publ_contact_author_phone       '+1 514 343 6283'
_publ_section_title
;
 Experimental Evidence for the All-Up Reactive Conformation of Chiral
 Rhodium(II) Carboxylate Catalysts: Enantioselective Synthesis of
 cis-Cyclopropane \a-Amino Acids
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              16383
_journal_page_last               16385
_journal_paper_doi               10.1021/ja9044955
_journal_volume                  131
_journal_year                    2009
_chemical_absolute_configuration rmad
_chemical_compound_source        'Synthesized by the authors. See text'
_chemical_formula_moiety         'C56 H44 Cl16 N4 O18 Rh2'
_chemical_formula_sum            'C56 H44 Cl16 N4 O18 Rh2'
_chemical_formula_weight         1833.97
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           90
_symmetry_cell_setting           tetragonal
_symmetry_space_group_name_Hall  'P 4ab 2ab'
_symmetry_space_group_name_H-M   'P 4 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.3018(7)
_cell_length_b                   22.3018
_cell_length_c                   21.4390(8)
_cell_measurement_reflns_used    16830
_cell_measurement_temperature    150
_cell_measurement_theta_max      57.10
_cell_measurement_theta_min      2.80
_cell_volume                     10663.1(5)
_computing_cell_refinement       'SAINT V7.34A (Bruker AXS, 2006b)'
_computing_data_collection       'APEX2 v2.1-0 (Bruker AXS, 2006a)'
_computing_data_reduction        'SAINT V7.34A (Bruker AXS, 2006b)'
_computing_molecular_graphics    'SHELXTL v6.12 (Bruker AXS, 2001)'
_computing_publication_material  'UdMX (Maris, 2004)'
_computing_structure_refinement  'SHELXL97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      150
_diffrn_detector_area_resol_mean 8.3
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker Microstar'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  'Helios optics'
_diffrn_radiation_source         'Rotating Anode'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.141
_diffrn_reflns_av_sigmaI/netI    0.0554
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            170380
_diffrn_reflns_theta_full        60.52
_diffrn_reflns_theta_max         60.52
_diffrn_reflns_theta_min         2.06
_diffrn_standards_decay_%        11.00
_diffrn_standards_interval_time  900
_diffrn_standards_number         919
_exptl_absorpt_coefficient_mu    6.590
_exptl_absorpt_correction_T_max  0.8206
_exptl_absorpt_correction_T_min  0.4842
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Sadabs (Sheldrick, 2004)'
_exptl_crystal_colour            Green
_exptl_crystal_density_diffrn    1.142
_exptl_crystal_description       Platelet
_exptl_crystal_F_000             3656
_exptl_crystal_size_max          0.10
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_platon_squeeze_details
;
Attempts to  model disordered solvent molecules
were unsuccessful. PLATON/SQUEEZE  was used to correct
the data for the presence of the disordered solvent.
A potential solvent volume of 4667.1 \%A^3^, 
43.8 % of the total unit-cell volume, was found.
1171 electrons per unit cell worth of scattering were located
in the void. The reported structure is based on the 
PLATON/SQUEEZE corrected data. The actual solvent content is
unknown, so several quantities calculated like empirical formula, density, 
absorption coefficient, F(000) etc. may be incorrect.

Ref:  Sluis, P. van der & Spek, A.L. (1990). Acta Cryst. A46, 194-201.
;
_refine_diff_density_max         1.474
_refine_diff_density_min         -0.515
_refine_diff_density_rms         0.110
_refine_ls_abs_structure_details 'Flack H D (1983), 3467 Friedel Pairs'
_refine_ls_abs_structure_Flack   0.14(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     440
_refine_ls_number_reflns         8022
_refine_ls_number_restraints     382
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.1177
_refine_ls_R_factor_gt           0.0877
_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^)+(0.1588P)^2^+6.0472P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2344
_refine_ls_wR_factor_ref         0.2546
_reflns_number_gt                5653
_reflns_number_total             8022
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            ja9044955_si_006.cif
_cod_data_source_block           cha181
_cod_depositor_comments
;
The following automatic conversions were performed:

'_geom_bond_publ_flag' value 'Y' changed to 'y' according to the
built-in table from CIF Core dictionary named 'cif_core.dic' version
2.4.1 from 2010-06-29 (82 times).

'_geom_angle_publ_flag' value 'Y'
changed to 'y' according to the built-in table from CIF Core
dictionary named 'cif_core.dic' version 2.4.1 from 2010-06-29 (196
times).

Automatic conversion script
Id: cif_fix_values 1715 2011-07-08 13:25:40Z adriana 
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_cod_database_code               4105352