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_1571886
_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         'C15 H15 Br O'
_chemical_formula_sum            'C15 H15 Br O'
_chemical_formula_weight         291.18
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-05-16
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.0877(6)
_cell_length_b                   10.7172(12)
_cell_length_c                   14.3707(11)
_cell_measurement_reflns_used    1546
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      21.3120
_cell_measurement_theta_min      2.3620
_cell_volume                     1399.6(2)
_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 1.000
_diffrn_measured_fraction_theta_max 0.883
_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      2.00  37.00   1.00   24.00    --   18.74  77.00 -60.00   35
  2  \w     21.00  87.00   1.00   24.00    --   18.74  57.00  90.00   66
  3  \w    -81.00  17.00   1.00   24.00    --  -18.93 -19.00-180.00   98
;
_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      0.0089053000
_diffrn_orient_matrix_UB_12      -0.0271056000
_diffrn_orient_matrix_UB_13      0.0446784000
_diffrn_orient_matrix_UB_21      -0.0459041000
_diffrn_orient_matrix_UB_22      0.0467915000
_diffrn_orient_matrix_UB_23      0.0194024000
_diffrn_orient_matrix_UB_31      -0.0624462000
_diffrn_orient_matrix_UB_32      -0.0382370000
_diffrn_orient_matrix_UB_33      -0.0079122000
_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  0.0288
_diffrn_reflns_av_unetI/netI     0.0611
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.883
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            5784
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.850
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.089
_diffrn_reflns_theta_min         2.371
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.919
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81946
_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    1.382
_exptl_crystal_description       block
_exptl_crystal_F_000             592
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.28
_refine_diff_density_max         0.623
_refine_diff_density_min         -0.491
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Flack x determined using 491 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.006(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     156
_refine_ls_number_reflns         3195
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.1258
_refine_ls_R_factor_gt           0.0565
_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^)+(0.0452P)^2^+0.9495P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1135
_refine_ls_wR_factor_ref         0.1420
_reflns_Friedel_coverage         0.683
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.806
_reflns_number_gt                1681
_reflns_number_total             3195
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02504k2.cif
_cod_data_source_block           20220516-zyk-09113
_cod_depositor_comments
'Adding full bibliography for 1571886--1571889.cif.'
_cod_database_code               1571886
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C15 H15 Br O'
_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 Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C4(H4A,H4B)
2.b Aromatic/amide H refined with riding coordinates:
 C15(H15), C11(H11), C13(H13), C12(H12)
2.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C)
2.d :
 C1(H1)
;
_shelx_res_checksum              7975
_shelx_hkl_checksum              62148
_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 1.103
_oxdiff_exptl_absorpt_empirical_full_min 0.913