Rearrangement of Hydroxylated Pinene Derivatives to Fenchone-Type Frameworks: Computational Evidence for Dynamically-Controlled Selectivity.
Blümel, Marcus; Nagasawa, Shota; Blackford, Katherine; Hare, Stephanie R.; Tantillo, Dean J.; Sarpong, Richmond; Journal of the American Chemical Society 140 (2018) 9291–9298; doi:10.1021/jacs.8b05804

data_4132720
_publ_section_title
;
 Rearrangement of Hydroxylated Pinene Derivatives to Fenchone-Type
 Frameworks: Computational Evidence for Dynamically-Controlled
 Selectivity.
;
_journal_issue                   29
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9291
_journal_page_last               9298
_journal_paper_doi               10.1021/jacs.8b05804
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         '2(C18 H21 F O2)'
_chemical_formula_sum            'C18 H21 F O2'
_chemical_formula_weight         288.35
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   7.64880(10)
_cell_length_b                   14.24190(10)
_cell_length_c                   28.2187(2)
_cell_measurement_reflns_used    25849
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      78.4990
_cell_measurement_theta_min      3.4470
_cell_volume                     3073.96(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.45f (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.45f (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.45f (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'ROD, Synergy Custom DW system, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0406
_diffrn_reflns_av_unetI/netI     0.0230
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            33070
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        74.000
_diffrn_reflns_theta_max         74.503
_diffrn_reflns_theta_min         3.476
_diffrn_source                   'Rotating-anode X-ray tube'
_exptl_absorpt_coefficient_mu    0.713
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80082
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.246
_exptl_crystal_description       block
_exptl_crystal_F_000             1232
_exptl_crystal_size_max          0.150
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.100
_refine_diff_density_max         0.147
_refine_diff_density_min         -0.170
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 2590 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.03(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     385
_refine_ls_number_reflns         6283
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0305
_refine_ls_R_factor_gt           0.0296
_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^)+(0.0371P)^2^+0.5722P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0754
_refine_ls_wR_factor_ref         0.0760
_reflns_Friedel_coverage         0.758
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                6103
_reflns_number_total             6283
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b05804_si_003.cif
_cod_data_source_block           sn003
_cod_database_code               4132720
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.901
_shelx_estimated_absorpt_t_max   0.932
_shelx_res_checksum              47712
_shelx_hkl_checksum              54388