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_4134426
_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_compound_source        'Leonidas Dimitrios Syntrivanis'
_chemical_formula_moiety         'C16 H25 N3 O'
_chemical_formula_sum            'C16 H25 N3 O'
_chemical_formula_weight         275.39
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2019-03-20
_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                 124.988(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.475(2)
_cell_length_b                   7.6092(8)
_cell_length_c                   12.4167(13)
_cell_measurement_reflns_used    9987
_cell_measurement_temperature    130
_cell_measurement_theta_max      69.914
_cell_measurement_theta_min      4.346
_cell_volume                     1584.9(3)
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      130
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.958
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Bruker Kappa Apex2'
_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  0.0248
_diffrn_reflns_av_unetI/netI     0.0204
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            10053
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.949
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         69.909
_diffrn_reflns_theta_min         4.346
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.575
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.6805
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0891 before and 0.0374 after correction.
The Ratio of minimum to maximum transmission is 0.9034.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.154
_exptl_crystal_description       block
_exptl_crystal_F_000             600
_exptl_crystal_recrystallization_method
'The material was recrystallised from ethanol by slow evaporation'
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.181
_refine_diff_density_min         -0.121
_refine_diff_density_rms         0.027
_refine_ls_abs_structure_details
;
 Flack x determined using 1292 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     184
_refine_ls_number_reflns         2855
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0280
_refine_ls_R_factor_gt           0.0280
_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^)+(0.0410P)^2^+0.4921P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0739
_refine_ls_wR_factor_ref         0.0740
_reflns_Friedel_coverage         0.832
_reflns_Friedel_fraction_full    0.965
_reflns_Friedel_fraction_max     0.938
_reflns_number_gt                2849
_reflns_number_total             2855
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01464_si_003.cif
_cod_data_source_block           lds224_130k_0m
_cod_depositor_comments
'Adding full bibliography for 4134426--4134427.cif.'
_cod_database_code               4134426
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C8(H8), C9(H9), C24(H24)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C17(H17A,H17B), C23(H23A,H23B), C30(H30A,H30B)
2.c Aromatic/amide H refined with riding coordinates:
 N6(H6), C6(H6A), C19(H19)
2.d X=CH2 refined with riding coordinates:
 N7(H7A,H7B)
2.e Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C22(H22A,H22B,H22C), C27(H27A,H27B,H27C)
;
_shelx_res_checksum              95941
_shelx_hkl_checksum              72005
_olex2_date_sample_data_collection 2019-03-15
_olex2_date_sample_submission    2019-02-27
_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_special_instructions 'No special instructions were received'