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_1571889
_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 ad
_chemical_formula_moiety         'C29 H28 O4'
_chemical_formula_sum            'C29 H28 O4'
_chemical_formula_weight         440.51
_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             2023-05-31
_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                 110.054(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.4747(4)
_cell_length_b                   6.58280(10)
_cell_length_c                   15.4889(4)
_cell_measurement_reflns_used    10545
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.3850
_cell_measurement_theta_min      3.9390
_cell_volume                     1194.81(6)
_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 0.999
_diffrn_measured_fraction_theta_max 0.997
_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    -72.00 -37.00   1.00    1.00    --    0.00 -38.00   0.00   35
  2  \w    -29.00  -2.00   1.00    1.00    --    0.00  88.00  74.00   27
  3  \w     -6.00  26.00   1.00    1.00    --    0.00 -38.00   0.00   32
  4  \w    -66.00 -31.00   1.00    1.00    --    0.00 -57.00 -60.00   35
  5  \w     29.00  64.00   1.00    1.00    --    0.00  57.00 -60.00   35
  6  \w      0.00  31.00   1.00    1.00    --    0.00  88.00  74.00   31
  7  \w    -16.00  19.00   1.00    1.00    --    0.00 -57.00 -60.00   35
  8  \w     24.00  60.00   1.00    1.00    --   54.00  77.00  90.00   36
  9  \w    -15.00  75.00   1.00    1.00    --   54.00 -57.00 -60.00   90
 10  \w     23.00 107.00   1.00    1.00    --   54.00-125.00 120.00   84
 11  \w     25.00  55.00   1.00    1.00    --   54.00  77.00-180.00   30
 12  \w     24.00  58.00   1.00    1.00    --   54.00  77.00 -90.00   34
 13  \w     24.00  65.00   1.00    1.00    --   54.00  77.00  60.00   41
 14  \w     64.00 120.00   1.00    1.00    --   54.00  77.00 -30.00   56
 15  \w     24.00  60.00   1.00    1.00    --   54.00  77.00 -60.00   36
 16  \w     27.00  57.00   1.00    1.00    --   54.00  77.00   0.00   30
 17  \w     -6.00  74.00   1.00    1.00    --   54.00 -57.00 120.00   80
 18  \w     73.00 123.00   1.00    1.00    --   54.00  77.00  60.00   50
 19  \w     78.00 118.00   1.00    1.00    --   54.00  77.00   0.00   40
 20  \w     80.00 113.00   1.00    1.00    --   54.00  77.00-180.00   33
 21  \w     78.00 122.00   1.00    1.00    --   54.00  77.00 -90.00   44
 22  \w     74.00 121.00   1.00    1.00    --   54.00  77.00-120.00   47
 23  \w     25.00  65.00   1.00    1.00    --   54.00  77.00-150.00   40
 24  \w     32.00  57.00   1.00    1.00    --   54.00  77.00-120.00   25
 25  \w     25.00  57.00   1.00    1.00    --   54.00  77.00  30.00   32
 26  \w     25.00  59.00   1.00    1.00    --   54.00  77.00 -30.00   34
 27  \w     -6.00  75.00   1.00    1.00    --   54.00 -57.00-150.00   81
 28  \w     87.00 124.00   1.00    1.00    --   54.00  77.00-150.00   37
 29  \w     24.00 101.00   1.00    1.00    --   54.00  77.00 150.00   77
 30  \w     83.00 109.00   1.00    1.00    --   54.00  77.00  90.00   26
 31  \w     26.00  58.00   1.00    1.00    --   54.00  77.00 120.00   32
 32  \w     78.00 105.00   1.00    1.00    --  108.00  77.00 120.00   27
 33  \w     78.00 104.00   1.00    1.00    --  108.00  77.00 -30.00   26
 34  \w     79.00 105.00   1.00    1.00    --  108.00  77.00-150.00   26
 35  \w    127.00 178.00   1.00    1.00    --  108.00  77.00  30.00   51
 36  \w     78.00 104.00   1.00    1.00    --  108.00  77.00  30.00   26
 37  \w     86.00 136.00   1.00    1.00    --  108.00  63.00 -60.00   50
 38  \w    134.00 178.00   1.00    1.00    --  108.00  77.00 -60.00   44
 39  \w    129.00 155.00   1.00    1.00    --  108.00  77.00-120.00   26
 40  \w     81.00 107.00   1.00    1.00    --  108.00  77.00-120.00   26
 41  \w     86.00 133.00   1.00    1.00    --  108.00  63.00   0.00   47
 42  \w    102.00 137.00   1.00    1.00    --  108.00 -77.00 150.00   35
 43  \w    121.00 177.00   1.00    1.00    --  108.00  77.00   2.29   56
 44  \w     39.00  80.00   1.00    1.00    --  108.00 -77.00 150.00   41
 45  \w     87.00 140.00   1.00    1.00    --  108.00  50.00-120.00   53
 46  \w     87.00 148.00   1.00    1.00    --  108.00  63.00-150.00   61
 47  \w    106.00 177.00   1.00    1.00    --  108.00 111.00 150.00   71
 48  \w     81.00 109.00   1.00    1.00    --  108.00-111.00  30.00   28
 49  \w     78.00 110.00   1.00    1.00    --  108.00  77.00-180.00   32
 50  \w     78.00 104.00   1.00    1.00    --  108.00  77.00 -60.00   26
 51  \w     94.00 152.00   1.00    1.00    --  108.00  50.00 -90.00   58
 52  \w    133.00 171.00   1.00    1.00    --  108.00  77.00 -90.00   38
 53  \w     80.00 105.00   1.00    1.00    --  108.00  77.00 -90.00   25
 54  \w     47.00  73.00   1.00    1.00    --  108.00 -63.00 -60.00   26
 55  \w     74.00 135.00   1.00    1.00    --  108.00 -77.00-120.00   61
 56  \w    109.00 146.00   1.00    1.00    --  108.00 -91.00  90.00   37
 57  \w    143.00 169.00   1.00    1.00    --  108.00  63.00-180.00   26
 58  \w     62.00 113.00   1.00    1.00    --  108.00-111.00 150.00   51
 59  \w     87.00 127.00   1.00    1.00    --  108.00  63.00-120.00   40
 60  \w     86.00 112.00   1.00    1.00    --  108.00  63.00 120.00   26
 61  \w     82.00 149.00   1.00    1.00    --  108.00  38.00  60.00   67
 62  \w     62.00  88.00   1.00    1.00    --  108.00 -91.00  90.00   26
 63  \w     86.00 122.00   1.00    1.00    --  108.00  63.00-180.00   36
 64  \w     37.00 100.00   1.00    1.00    --  108.00-111.00  90.00   63
 65  \w     45.00 111.00   1.00    1.00    --  108.00-111.00 -30.00   66
 66  \w     82.00 133.00   1.00    1.00    --  108.00  38.00 150.00   51
 67  \w    119.00 145.00   1.00    1.00    --  108.00  77.00  60.00   26
 68  \w    141.00 167.00   1.00    1.00    --  108.00  38.00  30.00   26
 69  \w     82.00 110.00   1.00    1.00    --  108.00  38.00  30.00   28
 70  \w     79.00 107.00   1.00    1.00    --  108.00  77.00  60.00   28
 71  \w    153.00 178.00   1.00    1.00    --  108.00  38.00 -60.00   25
 72  \w     82.00 112.00   1.00    1.00    --  108.00  38.00 -60.00   30
 73  \w    107.00 132.00   1.00    1.00    --  108.00  77.00 150.00   25
 74  \w     78.00 104.00   1.00    1.00    --  108.00  77.00  90.00   26
 75  \w     79.00 130.00   1.00    1.00    --  108.00 -50.00   0.00   51
 76  \w     42.00  67.00   1.00    1.00    --  108.00 -50.00   0.00   25
 77  \w     78.00 104.00   1.00    1.00    --  108.00  77.00 150.00   26
 78  \w     92.00 117.00   1.00    1.00    --  108.00  50.00-150.00   25
 79  \w     86.00 123.00   1.00    1.00    --  108.00  63.00  60.00   37
 80  \w     37.00  63.00   1.00    1.00    --  108.00-111.00-120.00   26
 81  \w     72.00 108.00   1.00    1.00    --  108.00-111.00-120.00   36
 82  \w     86.00 151.00   1.00    1.00    --  108.00  63.00  90.00   65
 83  \w    141.00 167.00   1.00    1.00    --  108.00  77.00 120.00   26
 84  \w     89.00 115.00   1.00    1.00    --  108.00  50.00 120.00   26
 85  \w    133.00 159.00   1.00    1.00    --  108.00  50.00 120.00   26
 86  \w     42.00 115.00   1.00    1.00    --  108.00 -25.00-150.00   73
 87  \w    133.00 173.00   1.00    1.00    --  108.00  77.00-150.00   40
 88  \w     88.00 173.00   1.00    1.00    --  108.00  55.00 -27.69   85
 89  \w     78.00 104.00   1.00    1.00    --  108.00  77.00   2.29   26
 90  \w     93.00 130.00   1.00    1.00    --  108.00  50.00  90.00   37
 91  \w     78.00 178.00   1.00    1.00    --  108.00  77.00 133.27  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0113107000
_diffrn_orient_matrix_UB_12      -0.1030473000
_diffrn_orient_matrix_UB_13      -0.0920258000
_diffrn_orient_matrix_UB_21      0.0610224000
_diffrn_orient_matrix_UB_22      0.1816463000
_diffrn_orient_matrix_UB_23      -0.0256106000
_diffrn_orient_matrix_UB_31      0.1158768000
_diffrn_orient_matrix_UB_32      -0.1056567000
_diffrn_orient_matrix_UB_33      0.0456690000
_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  0.0311
_diffrn_reflns_av_unetI/netI     0.0196
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            20099
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.538
_diffrn_reflns_theta_min         3.037
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.643
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.12259
_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    1.224
_exptl_crystal_description       block
_exptl_crystal_F_000             468
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.178
_refine_diff_density_min         -0.173
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 1820 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.06(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     302
_refine_ls_number_reflns         4544
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0387
_refine_ls_R_factor_gt           0.0364
_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^)+(0.0579P)^2^+0.0889P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0964
_refine_ls_wR_factor_ref         0.0999
_reflns_Friedel_coverage         0.826
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                4267
_reflns_number_total             4544
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02504k2.cif
_cod_data_source_block           20230531-zyk11032-1
_cod_depositor_comments
'Adding full bibliography for 1571886--1571889.cif.'
_cod_database_code               1571889
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C29 H28 O4'
_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:
 C17(H17)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C2(H2A,H2B)
2.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C21(H21), C12(H12), C26(H26), C28(H28), C15(H15), C14(H14),
 C23(H23), C20(H20), C25(H25)
2.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C18(H18A,H18B,H18C), C29(H29A,H29B,H29C)
2.e :
 C9(H9)
;
_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 5.483
_oxdiff_exptl_absorpt_empirical_full_min 0.457