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_7155892
_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 syn
_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     direct
_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                   6.2525(6)
_cell_length_b                   10.9938(10)
_cell_length_c                   24.717(2)
_cell_measurement_reflns_used    3904
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      26.543
_cell_measurement_theta_min      2.479
_cell_volume                     1699.0(3)
_computing_cell_refinement       'SAINT V6.36A (Bruker, 2016)'
_computing_data_collection       'Bruker SMART version 5.625 (Bruker, 2001)'
_computing_data_reduction        'SAINT V6.36A (Bruker, 2016)'
_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    'ShelXS-1997 (Sheldrick, 2008)'
_diffrn_ambient_temperature      150(2)
_diffrn_detector_area_resol_mean 8.366
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker SMART APEX CCD area detector'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0335
_diffrn_reflns_av_unetI/netI     0.0322
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            15135
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        27.500
_diffrn_reflns_theta_max         27.503
_diffrn_reflns_theta_min         2.027
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.074
_exptl_absorpt_correction_T_max  0.9803
_exptl_absorpt_correction_T_min  0.8723
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2007/2 (Bruker,2007) was used for absorption correction. wR2(int) was 0.0545 before and 0.0462 after correction. The Ratio of minimum to maximum transmission is 0.8898. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.174
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             656
_exptl_crystal_recrystallization_method
'slow evaporation of a pentane solution of the compound'
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.275
_refine_diff_density_min         -0.207
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 1302 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   1.7(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.184
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     203
_refine_ls_number_reflns         3900
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.184
_refine_ls_R_factor_all          0.0590
_refine_ls_R_factor_gt           0.0553
_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^)+(0.0526P)^2^+0.3481P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1194
_refine_ls_wR_factor_ref         0.1211
_reflns_Friedel_coverage         0.720
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                3681
_reflns_number_total             3900
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob02204b2.cif
_cod_data_source_block           cypspo
_cod_database_code               7155892
_nottingham_internal_coll_name   CYPSPO
_nottingham_internal_coll_number 8601
_nottingham_internal_coll_client MU/CJH
_nottingham_internal_coll_frame_width 0.3
_nottingham_internal_coll_user   pczwl
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'SMART APEX'
_nottingham_internal_process_user pczwl
_nottingham_internal_validation_date 29/8/2017
_nottingham_internal_validation_user pczwl
_shelx_shelxl_version_number     2017/1
_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), C4(H4), C11(H11), C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2a,H2b), C5(H5a,H5b), C7(H7a,H7b), C8(H8a,H8b), C10(H10a,H10b), C13(H13a,
 H13b)
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              77758
_olex2_date_sample_data_collection 2009-06-11
_olex2_date_sample_submission    2009-06-08
_olex2_submission_special_instructions 'No special instructions were received'