Ruthenium-Catalyzed Carboxylative Cyclization of 1,6-Diynes
Hahn Kim; Stephen D. Goble; Chulbom Lee; Journal of the American Chemical Society 129 (2007) 1030–1031; doi:10.1021/ja067336e

data_4109054
_publ_contact_author_address
;
Princeton University
Department of Chemistry
Princeton, NJ   08544-1009
USA
;
_publ_contact_author_email       cblee@princeton.edu
_publ_contact_author_fax         '(609) 258 6746'
_publ_contact_author_name        'Professor Chulbom Lee'
_publ_contact_author_phone       '(609) 258 6253'
_publ_section_title
;
 Ruthenium-Catalyzed Carboxylative Cyclization of 1,6-Diynes
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              1030
_journal_page_last               1031
_journal_paper_doi               10.1021/ja067336e
_journal_volume                  129
_journal_year                    2007
_chemical_absolute_configuration unk
_chemical_compound_source        'chemical synthesis'
_chemical_formula_iupac          'C18 H18 O6'
_chemical_formula_moiety         'C18 H18 O6'
_chemical_formula_structural     'C18 H18 O6'
_chemical_formula_sum            'C18 H18 O6'
_chemical_formula_weight         330.32
_chemical_name_systematic
;
(E)-5-Benzoyloxymethylenecyclohex-3-ene-1,1-dicarboxylic Acid
Dimethyl Ester
;
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      4
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             'October 24, 2005'
_audit_creation_method
;
SHELXL and manual editing of form.cif
;
_audit_update_record
;
Oct. 24, 2005  cbl006f.cif        Initial CIF created by DMH.

Oct. 24, 2005  Sent to Checkcif.  See cbl006f_checkcif.pdf for
                                  the alerts that were generated.

PLAT024_ALERT_4_B Merging of Friedel pairs is STRONGLY indicated.
REFLT03_ALERT_4_G MoKa measured Friedel data cannot be used to determine
                  absolute structure in a light-atom study EXCEPT under
                  VERY special conditions. It is preferred that Friedel
                  data is merged in such cases.

STRVA01_ALERT_4_C Flack test results are meaningless.
                  From the CIF: _refine_ls_abs_structure_Flack ... -0.01
                  From the CIF: _refine_ls_abs_structure_Flack_su . 0.90
PLAT032_ALERT_4_C Std. Uncertainty in Flack Parameter too High .... 0.90
PLAT850_ALERT_2_C Check Flack Parameter Exact Value 0.00 and su ... 0.90

PLAT390_ALERT_3_C Deviating Methyl C14 X-C-H Bond Angle .... 102.70 Deg.

 0 ALERT level A = In general, serious problem.
 1 ALERT level B = Potentially serious problem.
 4 ALERT level C = Check and explain.
 1 ALERT level G = General alerts. Check.

              PLAT024_ALERT_4_B, REFLT03_ALERT_4_G.  We have elected
              not to merge the Friedel pairs since:  (a) The C-H bond
              distances were significantly poorer with the merged
              (versus the unmerged) data, and (b) the standard uncer-
              tainties for all distances and angles were also poorer
              with the merged (versus the unmerged) data.

              STRVA01_ALERT_4_C, PLAT032_ALERT_4_C, PLAT850_ALERT_2_C.
              Yes, the Flack test results are meaningless and absolutely
              no attempt is made to state what the absolute structure of
              the molecule is.  These 3 alerts are totally consistent
              with the absence of a heavy atom or significant anomalous
              scatterer in the structure.  However, the target of this
              study is only the relative configuration of the molecule
              (and not the absolute structure).  Therefore, these alerts
              have no bearing.  The relative configuration of the
              molecule is uneqivocally determined regardless of these
              alerts, nor is there any decrease in the precision or
              certainty of the metrical results obtained.

              PLAT390_ALERT_3_C.  Deviations in the C-C-H angles at the
              methyl C(14) atom were noted, and were considered insuf-
              ficiently alarming to warrant restraints.  As indicated in
              the _geom_special_details section at the end of this file,
              the C(14) methyl group participates in a number of inter-
              molecular close contacts.  We elected to leave the methyl
              moiety unrestrained to allow it to better adjust to its
              surroundings.
              
A brief discussion of the data collection, data reduction, and structure
solution and refinement can be found near the middle of this file under
the following headings:

                      7. EXPERIMENTAL DATA FOR cbl006f
                      _exptl_special_details

                      8. REFINEMENT DATA FOR cbl006f
                      _refine_special_details

Also, please read the _geom_special_details section at the very bottom
of this file.  In that section, miscellaneous details on the structure
are provided as well as selected references that may be relevant to this
study.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 108.672(1)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   10.0350(2)
_cell_length_b                   6.3816(1)
_cell_length_c                   13.8107(3)
_cell_measurement_reflns_used    29751
_cell_measurement_temperature    200(2)
_cell_measurement_theta_max      27.51
_cell_measurement_theta_min      1.56
_cell_volume                     837.88(3)
_computing_cell_refinement       'DENZO-SMN (Otwinowski & Minor, 1997)'
_computing_data_collection       'COLLECT (Nonius, 1998)'
_computing_data_reduction        'DENZO-SMN (Otwinowski & Minor, 1997)'
_computing_molecular_graphics    'Siemens SHELXTL (Sheldrick, 1996)'
_computing_publication_material  'Siemens SHELXTL (Sheldrick, 1996)'
_computing_structure_refinement  'Siemens SHELXTL (Sheldrick, 1996)'
_computing_structure_solution    'Siemens SHELXTL (Sheldrick, 1996)'
_diffrn_ambient_temperature      200(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'Nonius KappaCCD'
_diffrn_measurement_method       '\w scans, 550 2.0\% rotations'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.043
_diffrn_reflns_av_sigmaI/netI    0.033
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            29751
_diffrn_reflns_theta_full        27.51
_diffrn_reflns_theta_max         27.51
_diffrn_reflns_theta_min         1.56
_diffrn_standards_decay_%        0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.099
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.309
_exptl_crystal_description       Needle
_exptl_crystal_F_000             348
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.230
_refine_diff_density_min         -0.162
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.01(90)
_refine_ls_extinction_coef       0.0477(49)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_all   1.090
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    refxyz
_refine_ls_matrix_type           full
_refine_ls_number_parameters     272
_refine_ls_number_reflns         3852
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.090
_refine_ls_restrained_S_gt       1.064
_refine_ls_R_factor_all          0.0546
_refine_ls_R_factor_gt           0.0439
_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^)+(0.0497P)^2^+0.0984P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.1092
_refine_ls_wR_factor_ref         0.0983
_reflns_number_gt                3311
_reflns_number_total             3852
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            ja067336esi20061215_051528.cif
_cod_data_source_block           cbl006f
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               4109054