Alkynyl Prins Carbocyclization Cascades for the Synthesis of Linear-Fused Heterocyclic Ring Systems
Hernandez, Jackson; Frontier, Alison; Chemical Science  (2022) –; doi:10.1039/D2SC04750K

data_1567946
_publ_section_title
;
 Alkynyl Prins Carbocyclization Cascades for the Synthesis of Linear-Fused
 Heterocyclic Ring Systems
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC04750K
_journal_year                    2022
_chemical_formula_moiety         'C31 H29 N O3'
_chemical_formula_sum            'C31 H29 N O3'
_chemical_formula_weight         463.55
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-05-31
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-05-31 deposited with the CCDC.	2022-11-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.7546(18)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.9276(3)
_cell_length_b                   5.55609(9)
_cell_length_c                   27.3254(5)
_cell_measurement_reflns_used    16462
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      78.7420
_cell_measurement_theta_min      3.2870
_cell_volume                     2389.99(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.54a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.54a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.54a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.973
_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   -119.00 -28.00   0.50    0.85    --  -47.32 -69.00 -75.00  182
  2  \w    -67.00  25.00   0.50    0.85    --  -47.32  69.00  56.00  184
  3  \w    -24.00  67.00   0.50    0.85    --   47.32 -69.00 -75.00  182
  4  \w    -79.00 -19.00   0.50    3.40    --  -91.75  69.00  56.00  120
  5  \w   -163.00 -72.00   0.50    3.40    --  -91.75 -69.00 -75.00  182
  6  \w     94.00 178.00   0.50    3.40    --  113.25  69.00  56.00  168
  7  \w     42.00  93.00   0.50    3.40    --  113.25 -69.00 -75.00  102
  8  \w   -119.00 -73.00   0.50    0.85    --  -47.32-125.00   0.00   92
  9  \w    -16.00  28.00   0.50    0.85    --  -47.32  19.00-180.00   88
 10  \w    -65.00 -19.00   0.50    3.40    --  -91.75  61.00-120.00   92
 11  \w    -65.00 -19.00   0.50    3.40    --  -91.75  61.00-180.00   92
 12  \w     42.00  79.00   0.50    3.40    --  113.25 -61.00 -30.00   74
 13  \w     42.00  79.00   0.50    3.40    --  113.25 -61.00  90.00   74
 14  \w    101.00 178.00   0.50    3.40    --  113.25  45.00 -30.00  154
 15  \w     42.00  79.00   0.50    3.40    --  113.25 -61.00   0.00   74
 16  \w     42.00  79.00   0.50    3.40    --  113.25 -61.00  60.00   74
 17  \w     42.00 111.00   0.50    3.40    --  113.25-125.00 -90.00  138
 18  \w    101.00 178.00   0.50    3.40    --  113.25  45.00  30.00  154
 19  \w    101.00 178.00   0.50    3.40    --  113.25  30.00-180.00  154
 20  \w    101.00 178.00   0.50    3.40    --  113.25  30.00   0.00  154
 21  \w     42.00 111.00   0.50    3.40    --  113.25-125.00 -60.00  138
 22  \w     42.00  79.00   0.50    3.40    --  113.25 -61.00-150.00   74
 23  \w     42.00  79.00   0.50    3.40    --  113.25 -61.00-180.00   74
 24  \w     42.00  79.00   0.50    3.40    --  113.25 -61.00 120.00   74
 25  \w     42.00 106.00   0.50    3.40    --  113.25 -94.00 -30.00  128
 26  \w     42.00 106.00   0.50    3.40    --  113.25 -94.00  60.00  128
 27  \w     33.00 120.00   0.50    0.85    --   47.32  57.00 150.00  174
 28  \w     33.00 120.00   0.50    0.85    --   47.32  57.00-150.00  174
 29  \w     25.00 120.00   0.50    0.85    --   47.32  77.00 -30.00  190
 30  \w     25.00  78.00   0.50    0.85    --   47.32  77.00-120.00  106
 31  \w     28.00 120.00   0.50    0.85    --   47.32  69.00  56.00  184
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0345688000
_diffrn_orient_matrix_UB_12      0.2149280000
_diffrn_orient_matrix_UB_13      0.0326147000
_diffrn_orient_matrix_UB_21      -0.0703214000
_diffrn_orient_matrix_UB_22      -0.0372696000
_diffrn_orient_matrix_UB_23      0.0322627000
_diffrn_orient_matrix_UB_31      0.0586405000
_diffrn_orient_matrix_UB_32      -0.1712230000
_diffrn_orient_matrix_UB_33      0.0339453000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.044
_diffrn_reflns_av_unetI/netI     0.0161
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            47366
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         80.341
_diffrn_reflns_theta_min         3.273
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.651
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63440
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.54a (Rigaku Oxford Diffraction, 2022)
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    1.288
_exptl_crystal_description       needle
_exptl_crystal_F_000             984
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.104
_exptl_crystal_size_min          0.077
_refine_diff_density_max         0.617
_refine_diff_density_min         -0.408
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.099
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     355
_refine_ls_number_reflns         9452
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.100
_refine_ls_R_factor_all          0.0762
_refine_ls_R_factor_gt           0.0706
_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^)+(0.0704P)^2^+1.9418P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1831
_refine_ls_wR_factor_ref         0.1865
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8533
_reflns_number_total             9452
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04750k2.cif
_cod_data_source_block           frojjh30
_cod_database_code               1567946
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.952
_shelx_estimated_absorpt_t_min   0.881
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6621(14)
 0.3379(14)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C16-C15 \\sim C16-C15'
 with sigma of 0.02
 C15-C14 \\sim C15'-C14'
 with sigma of 0.02
 C14-O1 \\sim C14'-O1'
 with sigma of 0.02
 C14-C13 \\sim C14'-C13'
 with sigma of 0.02
 C13-C12 \\sim C13'-C12
 with sigma of 0.02
 O1-C1 \\sim O1'-C1
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.2A with sigma of 0.005 and
sigma for terminal atoms of 0.01 within 1.2A
5. Others
 Sof(H1B)=Sof(H12C)=Sof(H12D)=Sof(O1')=Sof(C13')=Sof(H13C)=Sof(H13D)=Sof(C14')=
 Sof(H14')=Sof(C15')=Sof(H15C)=Sof(H15D)=1-FVAR(1)
 Sof(H1A)=Sof(H12A)=Sof(H12B)=Sof(O1)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(C14)=
 Sof(H14)=Sof(C15)=Sof(H15A)=Sof(H15B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C1(H1A), C1(H1B), C14(H14), C14'(H14')
6.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C12(H12A,H12B), C12(H12C,H12D), C13(H13A,H13B),
 C15(H15A,H15B), C13'(H13C,H13D), C15'(H15C,H15D)
6.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C17(H17), C20(H20), C21(H21), C23(H23),
 C24(H24), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30)
6.d Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C)
;
_shelx_res_checksum              10887
_shelx_hkl_checksum              29711
_olex2_submission_original_sample_id frojjh30
_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 1.719
_oxdiff_exptl_absorpt_empirical_full_min 0.664