Highly Z-Selective and Enantioselective Ring-Opening/Cross-Metathesis Catalyzed by a Resolved Stereogenic-at-Ru Complex
John Hartung; Robert H. Grubbs; Journal of the American Chemical Society 135 (2013) 10183–10185; doi:10.1021/ja4046422

data_4120123
_publ_contact_author_address
;
Beckman Institute
Caltech 139-74
Pasadena CA 91125
USA
;
_publ_contact_author_email       xray@caltech.edu
_publ_contact_author_name        'Xray Staff'
_publ_section_title
;
 Highly Z-Selective and Enantioselective Ring-Opening/Cross-Metathesis
 Catalyzed by a Resolved Stereogenic-at-Ru Complex
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10183
_journal_page_last               10185
_journal_paper_doi               10.1021/ja4046422
_journal_volume                  135
_journal_year                    2013
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H21 Br N2 O6'
_chemical_formula_sum            'C25 H21 Br N2 O6'
_chemical_formula_weight         525.35
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_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     dual
_audit_creation_date             2013-04-12
_audit_creation_method
;
  Olex2 1.2
  (compiled Mar 21 2013 11:17:50, GUI svn.r4446),
 SHELXL-2013,
 and manual edit
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.8772(3)
_cell_length_b                   15.7930(10)
_cell_length_c                   20.9413(12)
_cell_measurement_reflns_used    7125
_cell_measurement_temperature    100
_cell_measurement_theta_max      24.81
_cell_measurement_theta_min      2.58
_cell_volume                     2274.5(2)
_computing_cell_refinement       'SAINT V8.27B (Bruker-AXS, 2007)'
_computing_data_collection       'APEX2 2013.2-0 (Bruker-AXS, 2007)'
_computing_data_reduction        'SAINT V8.27B (Bruker-AXS, 2007)'
_computing_molecular_graphics    'DIAMOND 3 (Crystal Impact, 1999)'
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
 and SHELXTL (Bruker-AXS, 2007)
;
_computing_structure_refinement  'SHELXL-2013/2 (Sheldrick, 2013)'
_computing_structure_solution    'SHELXT (Sheldrick, 2012)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 8.33
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.930
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0777
_diffrn_reflns_av_unetI/netI     0.0925
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.930
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            34241
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.904
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         29.752
_diffrn_reflns_theta_min         1.945
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.853
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8351
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0856 before and 0.0789 after correction.
The Ratio of minimum to maximum transmission is 0.8351.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.534
_exptl_crystal_description       blade
_exptl_crystal_F_000             1072
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.672
_refine_diff_density_min         -0.473
_refine_diff_density_rms         0.080
_refine_ls_abs_structure_details
;
 Flack x determined using 1509 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.003(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     307
_refine_ls_number_reflns         5864
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0789
_refine_ls_R_factor_gt           0.0434
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0558
_refine_ls_wR_factor_ref         0.0614
_reflns_Friedel_coverage         0.716
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.870
_reflns_number_gt                4359
_reflns_number_total             5864
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja4046422_si_004.cif
_cod_data_source_block           jhh001
_cod_depositor_comments
;
The following automatic conversions were performed:

'_diffrn_source_target' value 'MO' changed to 'Mo' according to the
built-in table from CIF Core dictionary named 'cif_core.dic' version
2.4.1 from 2010-06-29.

Automatic conversion script
Id: cif_fix_values 2281 2013-09-26 08:29:07Z andrius 
;
_cod_database_code               4120123
_cod_database_fobs_code          4120123
_refine_ls_abs_structure_hooft   0.014(6)
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C16(H16A,H16B)
2.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C12(H12), C13(H13), C14(H14), C15(H15), C19(H19), C20(H20),
 C22(H22), C23(H23), C24(H24)
2.d X=CH2 refined with riding coordinates:
 C25(H25A,H25B)
;
_shelx_estimated_absorpt_t_max   0.930
_shelx_estimated_absorpt_t_min   0.720
_shelxl_version_number           2013-2