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_4132721
_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         'C23 H24 O2'
_chemical_formula_sum            'C23 H24 O2'
_chemical_formula_weight         332.42
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-03-01
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.6300(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.32690(10)
_cell_length_b                   7.68930(10)
_cell_length_c                   13.87280(10)
_cell_measurement_reflns_used    15701
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      78.2490
_cell_measurement_theta_min      5.4370
_cell_volume                     873.005(17)
_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 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -45.00  25.00   0.40    0.40    --    0.00 -88.00  14.00  175
  2  \w    -24.00  38.00   0.40    0.40    --    0.00  88.00 130.00  155
  3  \w   -174.00 -80.00   0.40    0.40    -- -100.00 -88.00  14.00  235
  4  \w     32.00 130.00   0.40    0.40    --  106.00 -88.00  14.00  245
  5  \w    -15.00  31.00   0.40    0.40    --    0.00 -99.00 -30.00  115
  6  \w    -15.00  31.00   0.40    0.40    --    0.00 -99.00-120.00  115
  7  \w    -77.00   7.00   0.40    0.40    --    0.00   0.00-150.00  210
  8  \w    -15.00  31.00   0.40    0.40    --    0.00 -99.00 150.00  115
  9  \w    -20.00  72.00   0.40    0.40    --    0.00  77.00-150.00  230
 10  \w   -170.00 -86.00   0.40    0.40    -- -100.00 -61.00  60.00  210
 11  \w    -72.00 -24.00   0.40    0.40    -- -100.00  30.00 120.00  120
 12  \w   -178.00 -94.00   0.40    0.40    -- -100.00 -15.00 -90.00  210
 13  \w   -177.00 -93.00   0.40    0.40    -- -100.00   0.00 -90.00  210
 14  \w   -112.00 -24.00   0.40    0.40    -- -100.00 111.00 150.00  220
 15  \w   -175.00 -91.00   0.40    0.40    -- -100.00 -45.00-120.00  210
 16  \w   -177.00 -95.00   0.40    0.40    -- -100.00 -30.00 120.00  205
 17  \w    -72.00 -24.00   0.40    0.40    -- -100.00  30.00 150.00  120
 18  \w   -175.00 -91.00   0.40    0.40    -- -100.00 -45.00-150.00  210
 19  \w   -177.00 -93.00   0.40    0.40    -- -100.00   0.00  60.00  210
 20  \w   -125.00 -27.00   0.40    0.40    -- -100.00  88.00 130.00  245
 21  \w   -177.00 -95.00   0.40    0.40    -- -100.00 -30.00-150.00  205
 22  \w   -172.00 -80.00   0.40    0.40    -- -100.00 -77.00  30.00  230
 23  \w   -120.00 -28.00   0.40    0.40    -- -100.00  77.00 120.00  230
 24  \w     92.00 176.00   0.40    0.40    --  106.00  61.00  60.00  210
 25  \w     30.00 108.00   0.40    0.40    --  106.00 -94.00  90.00  195
 26  \w     31.00  73.00   0.40    0.40    --  106.00 -45.00-150.00  105
 27  \w     30.00 108.00   0.40    0.40    --  106.00 -94.00 -30.00  195
 28  \w     31.00  73.00   0.40    0.40    --  106.00 -45.00   0.00  105
 29  \w     30.00 108.00   0.40    0.40    --  106.00 -94.00   0.00  195
 30  \w     30.00 108.00   0.40    0.40    --  106.00 -94.00 150.00  195
 31  \w     30.00 112.00   0.40    0.40    --  106.00-111.00-180.00  205
 32  \w     29.00  65.00   0.40    0.40    --  106.00 -30.00-150.00   90
 33  \w    100.00 178.00   0.40    0.40    --  106.00  30.00  30.00  195
 34  \w     30.00 108.00   0.40    0.40    --  106.00 -94.00 120.00  195
 35  \w     30.00 108.00   0.40    0.40    --  106.00 -94.00 -60.00  195
 36  \w     30.00 112.00   0.40    0.40    --  106.00-111.00  90.00  205
 37  \w     31.00  73.00   0.40    0.40    --  106.00 -45.00 120.00  105
 38  \w     27.00 113.00   0.40    0.40    --  106.00 -15.00 -30.00  215
 39  \w     30.00 112.00   0.40    0.40    --  106.00-111.00  60.00  205
 40  \w     81.00 177.00   0.40    0.40    --  106.00  88.00 130.00  240
 41  \w    -77.00   7.00   0.40    0.40    --    0.00 -38.00  60.00  210
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom DW system, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0258661000
_diffrn_orient_matrix_UB_12      0.0514294000
_diffrn_orient_matrix_UB_13      -0.1033507000
_diffrn_orient_matrix_UB_21      0.0776503000
_diffrn_orient_matrix_UB_22      0.1729462000
_diffrn_orient_matrix_UB_23      0.0409352000
_diffrn_orient_matrix_UB_31      0.1694944000
_diffrn_orient_matrix_UB_32      -0.0871929000
_diffrn_orient_matrix_UB_33      0.0201844000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0280
_diffrn_reflns_av_unetI/netI     0.0149
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            18444
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.784
_diffrn_reflns_theta_min         5.405
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.617
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90126
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.45f (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.265
_exptl_crystal_description       block
_exptl_crystal_F_000             356
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.127
_refine_diff_density_min         -0.159
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 1650 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     228
_refine_ls_number_reflns         3690
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0347
_refine_ls_R_factor_gt           0.0344
_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^)+(0.0430P)^2^+0.2432P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0895
_refine_ls_wR_factor_ref         0.0897
_reflns_Friedel_coverage         0.839
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.963
_reflns_number_gt                3651
_reflns_number_total             3690
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b05804_si_002.cif
_cod_data_source_block           MB2_014
_cod_database_code               4132721
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C23 O2 H25'
_shelx_estimated_absorpt_t_max   0.952
_shelx_estimated_absorpt_t_min   0.887
_reflns_odcompleteness_completeness 99.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C13(H13), C14(H14), C16(H16)
2.b Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C15(H15A,H15B), C17(H17A,H17B)
2.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C5(H5), C11(H11), C8(H8), C9(H9), C1(H1), C4(H4), C2(H2), C3(H3)
2.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C22(H22A,H22B,H22C)
;
_shelx_res_checksum              48739
_shelx_hkl_checksum              17637
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.680
_oxdiff_exptl_absorpt_empirical_full_min 0.683