Four-Step Access to the Sesquiterpene Natural Product Presilphiperfolan-1β-ol and Unnatural Derivatives via Supramolecular Catalysis.
Syntrivanis, Leonidas-Dimitrios; Némethová, Ivana; Schmid, Dario; Levi, Shani; Prescimone, Alessandro; Bissegger, Fabian; Major, Dan T.; Tiefenbacher, Konrad; Journal of the American Chemical Society 142 (2020) 5894–5900; doi:10.1021/jacs.0c01464

data_4134427
_publ_section_title
;
 Four-Step Access to the Sesquiterpene Natural Product
 Presilphiperfolan-1\b-ol and Unnatural Derivatives via Supramolecular
 Catalysis.
;
_journal_issue                   12
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5894
_journal_page_last               5900
_journal_paper_doi               10.1021/jacs.0c01464
_journal_volume                  142
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C15 H26 O'
_chemical_formula_sum            'C15 H26 O'
_chemical_formula_weight         222.36
_space_group_crystal_system      tetragonal
_space_group_IT_number           96
_space_group_name_Hall           'P 4nw 2abw'
_space_group_name_H-M_alt        'P 43 21 2'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-17
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   16.2888(11)
_cell_length_b                   16.2888(11)
_cell_length_c                   20.5020(15)
_cell_measurement_reflns_used    9093
_cell_measurement_temperature    130
_cell_measurement_theta_max      70.043
_cell_measurement_theta_min      3.466
_cell_volume                     5439.7(7)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'Apex2 (Bruker AXS, 2006)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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      130
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f & \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0426
_diffrn_reflns_av_unetI/netI     0.0195
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            37629
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.226
_diffrn_reflns_theta_min         3.465
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.491
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.6580
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0871 before and 0.0545 after correction.
The Ratio of minimum to maximum transmission is 0.8735.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.086
_exptl_crystal_description       block
_exptl_crystal_F_000             1984
_exptl_crystal_recrystallization_method
'The material was recrystallised from penthane by slow evaporation'
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.527
_refine_diff_density_min         -0.350
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 2021 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.10(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     309
_refine_ls_number_reflns         5077
_refine_ls_number_restraints     10
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0553
_refine_ls_R_factor_gt           0.0538
_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^)+(0.0652P)^2^+2.6290P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1403
_refine_ls_wR_factor_ref         0.1419
_reflns_Friedel_coverage         0.722
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.972
_reflns_number_gt                4913
_reflns_number_total             5077
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01464_si_002.cif
_cod_data_source_block           lds221_130k_0m
_cod_depositor_comments
'Adding full bibliography for 4134426--4134427.cif.'
_cod_original_cell_volume        5439.7(8)
_cod_database_code               4134427
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.917
_shelx_estimated_absorpt_t_min   0.895
_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. Restrained distances
 O1-H1A = O1-H1B = O2-H2A = O2-H2B
 0.95 with sigma of 0.02
 O1-H1A \\sim O1-H1B \\sim O2-H2A \\sim O2-H2B
 with sigma of 0.02
3. Others
 Fixed Sof: H2A(0.5) H2B(0.5) H1B(0.5) H1A(0.5)
 Fixed Uiso: H2A(0.05) H2B(0.05) H1B(0.05) H1A(0.05)
4.a Ternary CH refined with riding coordinates:
 C17(H17), C18(H18), C2(H2), C3(H3), C14(H14), C29(H29)
4.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C20(H20A,H20B), C23(H23A,H23B), C13(H13A,H13B), C27(H27A,H27B),
 C28(H28A,H28B), C12(H12A,H12B), C5(H5A,H5B), C7(H7A,H7B), C22(H22A,H22B)
4.c Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C25(H25A,H25B,H25C), C15(H15A,H15B,H15C), C30(H30A,H30B,
 H30C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C), C24(H24A,H24B,H24C), C10(H10A,
 H10B,H10C)
;
_shelx_res_checksum              90397
_shelx_hkl_checksum              37230
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a mylar loop in perfluoroether oil'
_olex2_submission_original_sample_id LDS221_130K
_olex2_submission_special_instructions 'No special instructions were received'