Origins of the Loss of Concertedness in Pericyclic Reactions: Theoretical Prediction and Direct Observation of Stepwise Mechanisms in [3 + 2] Thermal Cycloadditions
Silvia Vivanco; Begoña Lecea; Ana Arrieta; Pilar Prieto; Iñaki Morao; Anthony Linden; Fernando P. Cossío; Journal of the American Chemical Society 122 (2000) 6078–6092; doi:10.1021/ja9945360

data_4116054
_publ_contact_author_address
; Organisch-chemisches Institut
  Universit\"at Z\"urich
  Winterthurerstrasse 190
  CH-8057 Z\"urich
  Switzerland
;
_publ_contact_author_email       alinden@oci.unizh.ch
_publ_contact_author_fax         '41 1 635 6812'
_publ_contact_author_name        'Dr. Anthony Linden'
_publ_contact_author_phone       '41 1 635 4228'
_publ_section_title
;
 Origins of the Loss of Concertedness in Pericyclic Reactions: Theoretical
 Prediction and Direct Observation of Stepwise Mechanisms in [3 + 2]
 Thermal Cycloadditions
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6078
_journal_page_last               6092
_journal_paper_doi               10.1021/ja9945360
_journal_volume                  122
_journal_year                    2000
_chemical_formula_moiety         'C25 H24 N2 O5 '
_chemical_formula_sum            'C25 H24 N2 O5'
_chemical_formula_weight         432.47
_chemical_melting_point          411(1)
_chemical_name_systematic
; (2S,3R,4S)-5,5-diphenyl-2-methoxycarbonyl-3-(4-methoxyphenyl)-
4-nitropyrrolidine
;
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      19
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.797(2)
_cell_length_b                   22.824(4)
_cell_length_c                   8.768(3)
_cell_measurement_reflns_used    25
_cell_measurement_temperature    173(1)
_cell_measurement_theta_max      20.0
_cell_measurement_theta_min      18.0
_cell_volume                     2160.7(9)
_computing_cell_refinement
;
MSC/AFC Diffractometer Control Software (Molecular Structure
Corporation, 1991)
;
_computing_data_collection
;
MSC/AFC Diffractometer Control Software (Molecular Structure
Corporation, 1991)
;
_computing_data_reduction
;
TEXSAN PROCESS (Molecular Structure Corporation, 1989)
;
_computing_molecular_graphics    'ORTEPII (Johnson, 1976)'
_computing_publication_material
;
TEXSAN FINISH (Molecular Structure Corporation, 1989)
;
_computing_structure_refinement
;
TEXSAN LS (Molecular Structure Corporation, 1989)
;
_computing_structure_solution    'SHELXS86 direct methods (Sheldrick, 1990)'
_diffrn_ambient_temperature      173(1)
_diffrn_detector                 'scintillation counter'
_diffrn_measurement_device_type  'Rigaku AFC-5R diffractometer'
_diffrn_measurement_method       '\w--2\q scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'Rigaku rotating anode generator'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71069
_diffrn_reflns_av_R_equivalents  0.088
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -1
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -1
_diffrn_reflns_number            3333
_diffrn_reflns_theta_full        27.5
_diffrn_reflns_theta_max         27.5
_diffrn_reflns_theta_min         2.5
_diffrn_standards_decay_%        0
_diffrn_standards_interval_count 150
_diffrn_standards_number         3
_exptl_absorpt_coefficient_mu    0.0932
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.329
_exptl_crystal_description       prism
_exptl_crystal_F_000             912
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.45
_exptl_crystal_size_min          0.35
_refine_diff_density_max         0.21
_refine_diff_density_min         -0.17
_refine_ls_abs_structure_details 'absolute structure chosen arbitrarily'
_refine_ls_extinction_coef       0.0000011(1)
_refine_ls_extinction_method     'Zachariasen (1963)'
_refine_ls_goodness_of_fit_ref   1.767
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     294
_refine_ls_number_reflns         2594
_refine_ls_number_restraints     0
_refine_ls_R_factor_gt           0.0399
_refine_ls_shift/su_max          0.0002
_refine_ls_structure_factor_coef F
_refine_ls_weighting_details     1/[\s^2^(F~o~)+(0.005F~o~)^2^]
_refine_ls_weighting_scheme      sigma
_refine_ls_wR_factor_ref         0.0359
_reflns_number_gt                2594
_reflns_number_total             3219
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9945360_1.cif
_cod_data_source_block           endo-3bc_(L9801)
_cod_depositor_comments
;
The following automatic conversions were performed:

'_atom_sites_solution_hydrogens' value 'difmap and geom' was changed
to 'mixed'.

Automatic conversion script
Id: cif_fix_values 6452 2018-10-05 10:23:21Z andrius 
;
_cod_original_cell_volume        2160.7(8)
_cod_original_formula_sum        'C25 H24 N2 O5 '
_cod_database_code               4116054