Total synthesis of (–)-aritasone via the ultra-high pressure hetero-Diels-Alder dimerisation of (–)-pinocarvone
Uroos, Maliha; Pitt, Phillip; Harwood, Laurence Marius; Lewis, William; Blake, Alexander J.; Hayes, Christopher J. J; Org. Biomol. Chem.  (2017) –; doi:10.1039/C7OB02204B

data_7155890
_publ_section_title
;
 Total synthesis of (--)-aritasone via the ultra-high pressure
 hetero-Diels-Alder dimerisation of (--)-pinocarvone
;
_journal_name_full               'Org. Biomol. Chem.'
_journal_paper_doi               10.1039/C7OB02204B
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H28 O2'
_chemical_formula_sum            'C20 H28 O2'
_chemical_formula_weight         300.42
_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   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2017-08-29
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2017-08-29 deposited with the CCDC.
2017-09-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.3710(2)
_cell_length_b                   11.8296(3)
_cell_length_c                   13.3226(3)
_cell_measurement_reflns_used    29930
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      76.5227
_cell_measurement_theta_min      3.3146
_cell_volume                     1634.48(6)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      90(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 10.3613
_diffrn_detector_type            'Agilent Diffraction Atlas detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega   -5.00   51.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       43.9127  -38.0000  120.0000 56

  2 omega   -9.00   40.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       43.9127    0.0000  -30.0000 49

  3 omega   42.00  122.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       43.9127    0.0000  -30.0000 80

  4 omega   39.00   64.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000  -30.0000   90.0000 25

  5 omega   36.00   64.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000  -30.0000  -90.0000 28

  6 omega   74.00  105.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000  -95.0000 -150.0000 31

  7 omega   39.00   67.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000  -30.0000 -180.0000 28

  8 omega   84.00  110.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   61.0000   90.0000 26

  9 omega   75.00  111.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000 -111.0000  150.0000 36

 10 omega   43.00   69.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000  -45.0000 -180.0000 26

 11 omega   40.00   68.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000  -30.0000   30.0000 28

 12 omega   42.00   85.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000  -61.0000   90.0000 43

 13 omega   95.00  121.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000  -61.0000   90.0000 26

 14 omega  120.00  150.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   61.0000  120.0000 30

 15 omega   43.00   69.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000  -45.0000  120.0000 26

 16 omega   38.00   69.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000  -30.0000   60.0000 31

 17 omega   43.00   70.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000  -45.0000 -120.0000 27

 18 omega   96.00  151.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   45.0000    0.0000 55

 19 omega   37.00  112.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000 -111.0000  -30.0000 75

 20 omega  103.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   30.0000  -90.0000 55

 21 omega   43.00   77.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000  -45.0000  150.0000 34

 22 omega   36.00   69.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000  -30.0000  150.0000 33

 23 omega   48.00   74.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000  -45.0000   90.0000 26

 24 omega  101.00  139.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   30.0000   60.0000 38

 25 omega   37.00   69.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000  -95.0000   30.0000 32

 26 omega -112.00  -19.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -43.9127  -57.0000   30.0000 93

 27 omega -112.00  -19.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -43.9127  -57.0000  120.0000 93

 28 omega -115.00  -14.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -43.9127  -77.0000 -120.0000 101

 29 omega    2.00   98.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       43.9127 -125.0000    0.0000 96

 30 omega -131.00  -30.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -60.0000  -77.0000  -30.0000 101

 31 omega   36.00   69.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000  -30.0000 -150.0000 33

 32 omega   89.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   30.0000   90.0000 69

 33 omega   36.00   69.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000  -30.0000    0.0000 33

 34 omega   87.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   45.0000 -120.0000 71

 35 omega   89.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   30.0000  150.0000 69

 36 omega   83.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   61.0000 -180.0000 75

 37 omega   79.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   77.0000    0.0000 79

 38 omega   30.00  109.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000  -95.0000   60.0000 79

 39 omega   34.00  113.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000 -104.0000   10.0000 79

 40 omega   83.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   61.0000  150.0000 75

 41 omega   83.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   61.0000  -90.0000 75

 42 omega   38.00  140.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000  -77.0000 -180.0000 102

 43 omega   83.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   61.0000  -30.0000 75

 44 omega   79.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   77.0000   90.0000 79

 45 omega   89.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   30.0000  -30.0000 69

 46 omega -115.00  -14.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -43.9127  -77.0000    0.0000 101

 47 omega  -24.00   69.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       43.9127  -57.0000   30.0000 93

 48 omega    2.00   98.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       43.9127 -125.0000  -90.0000 96

 49 omega   14.00  115.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       43.9127   77.0000 -180.0000 101

 50 omega -131.00  -30.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -60.0000  -77.0000  150.0000 101

 51 omega -131.00  -30.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -60.0000  -77.0000   30.0000 101

 52 omega -131.00  -30.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -60.0000  -77.0000  -90.0000 101

 53 omega -131.00  -30.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -60.0000  -77.0000 -150.0000 101

 54 omega -131.00  -30.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -60.0000  -77.0000   90.0000 101

 55 omega   36.00  115.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000 -111.0000  -90.0000 79

 56 omega   83.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   61.0000  -60.0000 75

 57 omega   79.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   77.0000   30.0000 79

 58 omega   40.00   77.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000  -45.0000  -30.0000 37

 59 omega   79.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   77.0000 -120.0000 79

 60 omega   83.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   61.0000 -150.0000 75

 61 omega   79.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   77.0000  -30.0000 79

 62 omega   79.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   77.0000  120.0000 79

 63 omega   41.00  136.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000  -61.0000   60.0000 95

 64 omega   79.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   77.0000 -180.0000 79

 65 omega   79.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   77.0000   60.0000 79

 66 omega -115.00  -14.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -43.9127  -77.0000  120.0000 101

 67 omega -115.00  -23.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -43.9127  -38.0000 -120.0000 92

 68 omega -115.00  -14.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -43.9127  -77.0000  -60.0000 101

 69 omega   23.00  115.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       43.9127   38.0000   90.0000 92

 70 omega   83.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   61.0000   60.0000 75

 71 omega   83.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   61.0000 -120.0000 75

 72 omega   36.00  115.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000 -111.0000 -180.0000 79

 73 omega   79.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   77.0000  -90.0000 79

 74 omega   79.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   77.0000  150.0000 79

 75 omega   83.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   61.0000   30.0000 75

 76 omega   79.00   83.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      109.5000   77.0000  -60.0000 4
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.1063454000
_diffrn_orient_matrix_UB_12      0.0692312000
_diffrn_orient_matrix_UB_13      0.0521703000
_diffrn_orient_matrix_UB_21      -0.0795040000
_diffrn_orient_matrix_UB_22      0.0001555000
_diffrn_orient_matrix_UB_23      0.0977254000
_diffrn_orient_matrix_UB_31      0.0667698000
_diffrn_orient_matrix_UB_32      -0.1102660000
_diffrn_orient_matrix_UB_33      0.0330475000
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_wavelength_determination fundamental
_diffrn_reflns_av_R_equivalents  0.0294
_diffrn_reflns_av_unetI/netI     0.0093
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            47596
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.319
_diffrn_reflns_theta_min         5.000
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_current           0.8
_diffrn_source_power             0.04
_diffrn_source_target            Cu
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.593
_exptl_absorpt_correction_T_max  1.443
_exptl_absorpt_correction_T_min  0.860
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.221
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             656
_exptl_crystal_size_max          0.3387
_exptl_crystal_size_mid          0.185
_exptl_crystal_size_min          0.1329
_refine_diff_density_max         0.209
_refine_diff_density_min         -0.169
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 1430 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     203
_refine_ls_number_reflns         3410
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0282
_refine_ls_R_factor_gt           0.0278
_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^)+(0.0476P)^2^+0.3068P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0751
_refine_ls_wR_factor_ref         0.0754
_reflns_Friedel_coverage         0.745
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                3355
_reflns_number_total             3410
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob02204b2.cif
_cod_data_source_block           mucjhn
_cod_database_code               7155890
_nottingham_internal_coll_name   MUCJHN
_nottingham_internal_coll_number 11226
_nottingham_internal_coll_client MU/CJH
_nottingham_internal_coll_user   pczwl
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument SuperNova
_nottingham_internal_process_user pczwl
_nottingham_internal_validation_date 29/8/2017
_nottingham_internal_validation_user pczwl
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C20 H28 O2'
_chemical_oxdiff_usercomment
'MUCJHN #11226 IN FOMBLIN FILM ON MICROMOUNT FOR MU/CJH'
_reflns_odcompleteness_completeness 98.60
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     77.17
_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:
 C3(H3), C5(H5), C10(H10), C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C7(H7A,H7B), C8(H8A,H8B), C13(H13A,H13B), C15(H15A,H15B),
 C18(H18A,H18B)
2.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C)
;
_shelx_res_checksum              87190
_olex2_submission_special_instructions 'No special instructions were received'