Acceleration of an Aromatic Claisen Rearrangement via a Designed Spiroligozyme Catalyst that Mimics the Ketosteroid Isomerase Catalytic Dyad.
Parker, Matthew F. L.; Osuna, Sílvia; Bollot, Guillaume; Vaddypally, Shivaiah; Zdilla, Michael J.; Houk, K. N.; Schafmeister, Christian E.; Journal of the American Chemical Society 136 (2014) 3817–3827; doi:10.1021/ja409214c

data_4121407
_publ_section_title
;
 Acceleration of an Aromatic Claisen Rearrangement via a Designed
 Spiroligozyme Catalyst that Mimics the Ketosteroid Isomerase Catalytic
 Dyad.
;
_journal_issue                   10
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3817
_journal_page_last               3827
_journal_paper_doi               10.1021/ja409214c
_journal_volume                  136
_journal_year                    2014
_chemical_absolute_configuration syn
_chemical_formula_moiety         '[C27 H29 N4 O7] . 2 [H2 O]'
_chemical_formula_sum            'C27 H33 N4 O9'
_chemical_formula_weight         557.57
_chemical_name_systematic
;
 ?
;
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_method           SHELXL-2013
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.1661(4)
_cell_length_b                   15.0421(9)
_cell_length_c                   29.2010(17)
_cell_measurement_reflns_used    9797
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.892
_cell_measurement_theta_min      2.79
_cell_volume                     2708.4(3)
_computing_cell_refinement
'CELL_NOW (Sheldrick, 2008), SAINT (Bruker AXS)'
_computing_data_collection       'COSMO (Bruker AXS)'
_computing_data_reduction        'TWINABS (Bruker AXS)'
_computing_publication_material  'APEX2 (Bruker AXS)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_solution    'SHELXL-2013 (Sheldrick, 2013)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8.333
_diffrn_measured_fraction_theta_full 0.914
_diffrn_measured_fraction_theta_max 0.937
_diffrn_measurement_device_type  'Bruker KAPPA APEX II DUO'
_diffrn_measurement_method       'omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0336
_diffrn_reflns_Laue_measured_fraction_full 0.914
_diffrn_reflns_Laue_measured_fraction_max 0.937
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            9302
_diffrn_reflns_point_group_measured_fraction_full 0.890
_diffrn_reflns_point_group_measured_fraction_max 0.912
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         1.395
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    0.104
_exptl_absorpt_correction_T_max  0.745620
_exptl_absorpt_correction_T_min  0.598358
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 14939 Corrected reflections written to file
 Reflections merged according to point-group 2/m   
 Single reflections that also occur in composites not omitted
 Minimum and maximum apparent transmission:  0.598358  0.745620
 Additional spherical absorption correction applied with mu*r =  0.2000
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.367
_exptl_crystal_description       needle
_exptl_crystal_F_000             1180
_exptl_crystal_size_max          0.240
_exptl_crystal_size_mid          0.080
_exptl_crystal_size_min          0.024
_refine_diff_density_max         0.306
_refine_diff_density_min         -0.199
_refine_diff_density_rms         0.041
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   -0.5(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     406
_refine_ls_number_reflns         9302
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.0436
_refine_ls_R_factor_gt           0.0364
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0478P)^2^+0.5937P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0836
_refine_ls_wR_factor_ref         0.0875
_reflns_Friedel_coverage         0.680
_reflns_Friedel_fraction_full    0.856
_reflns_Friedel_fraction_max     0.878
_reflns_number_gt                8370
_reflns_number_total             9302
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja409214c_si_002.cif
_cod_data_source_block           BPC1
_cod_database_code               4121407
_shelx_estimated_absorpt_t_min   0.976
_shelx_estimated_absorpt_t_max   0.998
_shelxl_version_number           2013-2
_shelx_res_checksum              94007
_shelx_hkl_checksum              31924