Catalytic asymmetric intramolecular propargylation of cyclopropanols to access the cuparane core.
Zhao, Yankun; Yan, Hongya; Zhang, Yulian; Zhou, Tao; Tian, Mengxing; Zhang, Chongzhou; Yuan, Shan; Qiu, Hanyue; He, Ling; Zhang, Min; Chemical science 15 (2024) 10963–10968; doi:10.1039/d4sc02504k

data_1571888
_publ_section_title
;
 Catalytic asymmetric intramolecular propargylation of cyclopropanols to
 access the cuparane core.
;
_journal_issue                   28
_journal_name_full               'Chemical science'
_journal_page_first              10963
_journal_page_last               10968
_journal_paper_doi               10.1039/d4sc02504k
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C25 H35 N3 O2'
_chemical_formula_sum            'C25 H35 N3 O2'
_chemical_formula_weight         409.56
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-10-27
_audit_creation_method
;
Olex2 1.5
(compiled 2021.10.07 svn.r9718050b for OlexSys, GUI svn.r6410)
;
_audit_update_record
;
2023-12-22 deposited with the CCDC.	2024-06-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.520(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.5199(3)
_cell_length_b                   8.9739(5)
_cell_length_c                   19.7834(10)
_cell_measurement_reflns_used    6517
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.5390
_cell_measurement_theta_min      3.8360
_cell_volume                     1150.02(10)
_computing_cell_refinement       'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0892
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.913
_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     36.00  61.00   1.00   15.32    --   18.74 -99.00 -30.00   25
  2  \w    -39.00  49.00   1.00   15.32    --   18.74 -77.00 150.00   88
  3  \w      1.00  87.00   1.00   15.32    --   18.74  57.00-150.00   86
  4  \w     -3.00  84.00   1.00   15.32    --   18.74  57.00 120.00   87
  5  \w      5.00  86.00   1.00   15.32    --   18.74  57.00 -60.00   81
  6  \w    -38.00  49.00   1.00   15.32    --   18.74 -77.00  60.00   87
  7  \w    -11.00  19.00   1.00   15.32    --   18.74  77.00  30.00   30
  8  \w    -36.00  37.00   1.00   15.32    --   18.74 -57.00 -60.00   73
  9  \w    -40.00  23.00   1.00   15.32    --  -18.93  57.00 -90.00   63
 10  \w    -78.00  -7.00   1.00   15.32    --  -18.93 -38.00 -30.00   71
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0704034000
_diffrn_orient_matrix_UB_12      -0.0478892000
_diffrn_orient_matrix_UB_13      0.0141760000
_diffrn_orient_matrix_UB_21      0.0720960000
_diffrn_orient_matrix_UB_22      -0.0098760000
_diffrn_orient_matrix_UB_23      0.0293054000
_diffrn_orient_matrix_UB_31      -0.0427449000
_diffrn_orient_matrix_UB_32      0.0621151000
_diffrn_orient_matrix_UB_33      0.0155886000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0352
_diffrn_reflns_av_unetI/netI     0.0444
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.913
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            16343
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.882
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.173
_diffrn_reflns_theta_min         3.421
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.075
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52110
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.117a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.183
_exptl_crystal_description       block
_exptl_crystal_F_000             444
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.159
_refine_diff_density_min         -0.198
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1449 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.3(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.141
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     273
_refine_ls_number_reflns         5469
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.141
_refine_ls_R_factor_all          0.0748
_refine_ls_R_factor_gt           0.0498
_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^)+(0.0622P)^2^+0.0916P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1328
_refine_ls_wR_factor_ref         0.1471
_reflns_Friedel_coverage         0.822
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.847
_reflns_number_gt                4023
_reflns_number_total             5469
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02504k2.cif
_cod_data_source_block           20221027-zyk-py-cy-me
_cod_depositor_comments
'Adding full bibliography for 1571886--1571889.cif.'
_cod_database_code               1571888
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C25 H35 N3 O2'
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.977
_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:
 C008(H008), C00C(H00C), C00F(H00F), C00G(H00G), C00H(H00H), C00J(H00K)
2.b Secondary CH2 refined with riding coordinates:
 C00K(H00L,H00M), C00L(H00N,H00O), C00M(H00P,H00Q), C00N(H00R,H00S), C00P(H00W,
 H00X), C00Q(H00Y,H), C00R(H00Z,HA), C00S(H00,HB), C00T(H1,HC), C00U(H2,HD)
2.c Aromatic/amide H refined with riding coordinates:
 C00B(H00B), C00D(H00D), C00E(H00E)
2.d Idealised Me refined as rotating group:
 C00I(H00A,H00I,H00J), C00O(H00T,H00U,H00V)
;
_shelx_res_checksum              60079
_shelx_hkl_checksum              37046
_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 1.444
_oxdiff_exptl_absorpt_empirical_full_min 0.503