Kinetic resolution of 1-(1-alkynyl)cyclopropyl ketones <i>via</i> gold-catalyzed divergent (4 + 4) cycloadditions: stereoselective access to furan fused eight-membered heterocycles.
Wang, Xunhua; Lv, Ruifeng; Li, Xiaoxun; Chemical science 15 (2024) 9361–9368; doi:10.1039/d4sc02763a

data_1571690
_publ_section_title
;
 Kinetic resolution of 1-(1-alkynyl)cyclopropyl ketones <i>via</i>
 gold-catalyzed divergent (4 + 4) cycloadditions: stereoselective access
 to furan fused eight-membered heterocycles.
;
_journal_issue                   24
_journal_name_full               'Chemical science'
_journal_page_first              9361
_journal_page_last               9368
_journal_paper_doi               10.1039/d4sc02763a
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C40 H32 O6'
_chemical_formula_sum            'C40 H32 O6'
_chemical_formula_weight         608.65
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-02-25
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-10-18 deposited with the CCDC.	2024-05-14 downloaded from the CCDC.
;
_cell_angle_alpha                78.461(2)
_cell_angle_beta                 62.446(3)
_cell_angle_gamma                64.147(3)
_cell_formula_units_Z            2
_cell_length_a                   12.1952(3)
_cell_length_b                   12.2266(3)
_cell_length_c                   12.7568(4)
_cell_measurement_reflns_used    18408
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      76.1750
_cell_measurement_theta_min      3.9450
_cell_volume                     1517.58(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      173(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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     26.00  52.00   1.00    0.10    --   48.45  77.00 120.00   26
  2  \w     84.00 173.00   1.00    0.45    --  106.49  77.00 120.00   89
  3  \w     90.00 175.00   1.00    0.45    --  106.49  77.00  90.00   85
  4  \w     37.00  63.00   1.00    0.10    --   54.00  76.00  62.13   26
  5  \w     95.00 126.00   1.00    0.10    --   54.00  76.00  62.13   31
  6  \w    105.00 131.00   1.00    0.10    --   62.00  75.00  39.83   26
  7  \w     40.00  68.00   1.00    0.10    --   62.00  75.00  39.83   28
  8  \w     35.00  65.00   1.00    0.10    --   54.00  74.00 -43.15   30
  9  \w     66.00  92.00   1.00    0.10    --   54.00  74.00 -43.15   26
 10  \w    103.00 135.00   1.00    0.10    --   62.00  73.00  -4.58   32
 11  \w     41.00  75.00   1.00    0.10    --   62.00  73.00  -4.58   34
 12  \w     43.00  68.00   1.00    0.10    --   62.00  71.00 130.37   25
 13  \w     45.00  70.00   1.00    0.10    --   66.00  73.00  64.37   25
 14  \w     45.00  71.00   1.00    0.10    --   62.00  71.00 152.13   26
 15  \w     38.00  70.00   1.00    0.10    --   58.00  71.00 101.17   32
 16  \w     52.00  77.00   1.00    0.10    --   48.45  65.00 -94.00   25
 17  \w     43.00  71.00   1.00    0.10    --   48.45  38.00-180.00   28
 18  \w    139.00 178.00   1.00    0.45    --  106.49  38.00-120.00   39
 19  \w    109.00 172.00   1.00    0.45    --  106.49  77.00-180.00   63
 20  \w     99.00 130.00   1.00    0.45    --  106.49  38.00-120.00   31
 21  \w    121.00 157.00   1.00    0.45    --  106.49  38.00-180.00   36
 22  \w     89.00 173.00   1.00    0.45    --  106.49  65.00 -94.00   84
 23  \w     97.00 177.00   1.00    0.45    --  106.49  38.00 -30.00   80
 24  \w     99.00 158.00   1.00    0.45    --  106.49  57.00   0.00   59
 25  \w     95.00 177.00   1.00    0.45    --  106.49  57.00  60.00   82
 26  \w    145.00 173.00   1.00    0.45    --  106.49  19.00  30.00   28
 27  \w    107.00 133.00   1.00    0.45    --  106.49  19.00  30.00   26
 28  \w    111.00 147.00   1.00    0.45    --  106.49  19.00 -90.00   36
 29  \w     37.00  99.00   1.00    0.45    --  106.49 -99.00 -60.00   62
 30  \w     75.00 101.00   1.00    0.45    --  106.49 -99.00 -90.00   26
 31  \w     79.00 111.00   1.00    0.45    --  106.49-125.00-150.00   32
 32  \w     77.00 107.00   1.00    0.45    --  106.49-105.00-153.81   30
 33  \w     46.00  72.00   1.00    0.45    --  106.49-125.00-150.00   26
 34  \w     78.00 104.00   1.00    0.45    --  106.49 -99.00-150.00   26
 35  \w     35.00  60.00   1.00    0.45    --  106.49 -99.00 -90.00   25
 36  \w     34.00  70.00   1.00    0.45    --  106.49 -99.00-150.00   36
 37  \w     79.00 105.00   1.00    0.45    --  106.49 -99.00   0.00   26
 38  \w     60.00 101.00   1.00    0.45    --  106.49-125.00  90.00   41
 39  \w     42.00  91.00   1.00    0.45    --  106.49 -99.00 150.00   49
 40  \w     34.00 106.00   1.00    0.45    --  106.49 -99.00  90.00   72
 41  \w     80.00 105.00   1.00    0.45    --  106.49 -99.00  60.00   25
 42  \w     34.00  69.00   1.00    0.45    --  106.49 -99.00  60.00   35
 43  \w     34.00  67.00   1.00    0.45    --  106.49 -99.00   0.00   33
 44  \w     75.00 100.00   1.00    0.45    --  106.49 -99.00 -30.00   25
 45  \w     34.00  64.00   1.00    0.45    --  106.49 -57.00 -30.00   30
 46  \w     35.00  73.00   1.00    0.45    --  106.49 -77.00-150.00   38
 47  \w     78.00 104.00   1.00    0.45    --  106.49 -77.00-150.00   26
 48  \w     35.00  80.00   1.00    0.45    --  106.49 -77.00  90.00   45
 49  \w     52.00  77.00   1.00    0.45    --  106.49 -65.00 129.00   25
 50  \w     41.00  66.00   1.00    0.10    --   48.45 -65.00 129.00   25
 51  \w    -22.00  23.00   1.00    0.10    --   48.45 -65.00 129.00   45
 52  \w    -13.00  21.00   1.00    0.10    --   18.00  96.00  92.38   34
 53  \w    -14.00  13.00   1.00    0.10    --   18.00  99.00 -48.45   27
 54  \w    -20.00   9.00   1.00    0.10    --   14.00 102.00-156.20   29
 55  \w     12.00  37.00   1.00    0.10    --   42.00  92.00-133.87   25
 56  \w      3.00  38.00   1.00    0.10    --   30.00  86.00  70.46   35
 57  \w     -1.00  25.00   1.00    0.10    --  -34.00  95.00  14.86   26
 58  \w    -65.00  -4.00   1.00    0.10    --  -34.00  95.00  14.86   61
 59  \w    -63.00  16.00   1.00    0.10    --  -48.45  65.00 -94.00   79
 60  \w    -77.00 -17.00   1.00    0.45    --  -86.25  65.00 -94.00   60
 61  \w    -64.00 -15.00   1.00    0.45    --  -86.25  57.00  30.00   49
 62  \w    -99.00 -74.00   1.00    0.10    --  -48.45 -65.00 129.00   25
 63  \w    -52.00 -26.00   1.00    0.10    --  -48.45 -77.00 120.00   26
 64  \w    -52.00 -26.00   1.00    0.10    --  -48.45 -77.00   0.00   26
 65  \w    -56.00 -26.00   1.00    0.10    --  -48.45 -77.00 -30.00   30
 66  \w    -55.00 -26.00   1.00    0.10    --  -48.45 -77.00 -60.00   29
 67  \w    -58.00 -27.00   1.00    0.10    --  -48.45 -77.00 -90.00   31
 68  \w    -57.00 -26.00   1.00    0.10    --  -48.45 -77.00-150.00   31
 69  \w   -157.00-117.00   1.00    0.45    --  -86.25 -60.00 -91.38   40
 70  \w    -89.00 -63.00   1.00    0.45    --  -86.25 -77.00-120.00   26
 71  \w    -88.00 -63.00   1.00    0.45    --  -86.25 -77.00 -60.00   25
 72  \w   -110.00 -63.00   1.00    0.45    --  -86.25 -77.00-180.00   47
 73  \w   -150.00-110.00   1.00    0.45    --  -86.25 -77.00-120.00   40
 74  \w   -157.00-123.00   1.00    0.45    --  -86.25 -77.00-180.00   34
 75  \w    -89.00 -64.00   1.00    0.45    --  -86.25 -77.00  30.00   25
 76  \w    -89.00 -63.00   1.00    0.45    --  -86.00 -76.00  74.09   26
 77  \w    -57.00 -31.00   1.00    0.10    --  -54.00 -77.00 172.30   26
 78  \w   -111.00 -63.00   1.00    0.45    --  -86.25 -77.00 120.00   48
 79  \w   -159.00-106.00   1.00    0.45    --  -86.00 -76.00  74.09   53
 80  \w    -89.00 -64.00   1.00    0.45    --  -86.25 -76.00  91.93   25
 81  \w    -92.00 -64.00   1.00    0.45    --  -86.25 -76.00   8.02   28
 82  \w   -140.00-112.00   1.00    0.45    --  -86.25 -76.00  91.93   28
 83  \w   -156.00-116.00   1.00    0.45    --  -86.25 -76.00   8.02   40
 84  \w   -155.00-130.00   1.00    0.45    --  -86.25 -76.00 -44.11   25
 85  \w    -86.00 -51.00   1.00    0.45    --  -74.00 -76.00-138.74   35
 86  \w    -82.00 -56.00   1.00    0.45    --  -78.00 -75.00-145.79   26
 87  \w    -65.00 -39.00   1.00    0.10    --  -62.00 -76.00-115.34   26
 88  \w   -101.00 -65.00   1.00    0.45    --  -86.25 -74.00 -83.94   36
 89  \w   -153.00-105.00   1.00    0.45    --  -86.00 -74.00 -25.68   48
 90  \w    -69.00 -44.00   1.00    0.10    --  -66.00 -74.00-135.85   25
 91  \w    -89.00 -64.00   1.00    0.45    --  -86.25 -76.00 -44.11   25
 92  \w    -97.00 -64.00   1.00    0.45    --  -86.00 -74.00 -25.68   33
 93  \w    -96.00 -64.00   1.00    0.45    --  -86.25 -75.00 -14.62   32
 94  \w    -82.00 -56.00   1.00    0.45    --  -78.00 -75.00  74.14   26
 95  \w    -90.00 -65.00   1.00    0.45    --  -86.25 -74.00 139.14   25
 96  \w    -93.00 -67.00   1.00    0.45    --  -86.25 -73.00 151.99   26
 97  \w    -85.00 -60.00   1.00    0.45    --  -82.00 -74.00  50.90   25
 98  \w    -90.00 -65.00   1.00    0.45    --  -86.25 -73.00  39.56   25
 99  \w    -70.00 -41.00   1.00    0.10    --  -62.00 -73.00 141.82   29
100  \w    -80.00 -54.00   1.00    0.45    --  -74.00 -73.00  45.70   26
101  \w    -66.00 -41.00   1.00    0.10    --  -62.00 -73.00 -84.91   25
102  \w    -89.00 -59.00   1.00    0.45    --  -78.00 -72.00-106.95   30
103  \w   -125.00 -99.00   1.00    0.10    --  -66.00 -74.00-135.85   26
104  \w   -136.00-110.00   1.00    0.45    --  -86.25 -72.00-170.48   26
105  \w    -90.00 -65.00   1.00    0.45    --  -86.25 -72.00-170.48   25
106  \w    -91.00 -66.00   1.00    0.45    --  -86.25 -72.00-108.38   25
107  \w   -102.00 -65.00   1.00    0.45    --  -86.25 -72.00  30.29   37
108  \w   -149.00-123.00   1.00    0.45    --  -86.25 -72.00  30.29   26
109  \w    -83.00 -57.00   1.00    0.45    --  -78.00 -72.00 157.55   26
110  \w    -91.00 -66.00   1.00    0.45    --  -86.25 -70.00 154.83   25
111  \w   -120.00 -94.00   1.00    0.45    --  -86.25 -70.00 154.83   26
112  \w    -71.00 -46.00   1.00    0.10    --  -66.00 -70.00 113.37   25
113  \w    -74.00 -48.00   1.00    0.10    --  -66.00 -70.00 162.46   26
114  \w   -129.00-103.00   1.00    0.10    --  -66.00 -70.00 113.37   26
115  \w    -72.00 -47.00   1.00    0.10    --  -66.00 -70.00  -7.66   25
116  \w    -71.00 -46.00   1.00    0.10    --  -66.00 -69.00 -62.12   25
117  \w    -92.00 -66.00   1.00    0.45    --  -86.25 -70.00-140.53   26
118  \w    -75.00 -50.00   1.00    0.45    --  -70.00 -69.00 -91.25   25
119  \w   -101.00 -68.00   1.00    0.45    --  -86.25 -69.00 -47.64   33
120  \w   -156.00-130.00   1.00    0.45    --  -86.25 -69.00  85.70   26
121  \w   -101.00 -67.00   1.00    0.45    --  -86.25 -69.00  85.70   34
122  \w    -76.00 -47.00   1.00    0.10    --  -66.00 -68.00  51.72   29
123  \w   -150.00-114.00   1.00    0.45    --  -86.25 -65.00 129.00   36
124  \w   -104.00 -68.00   1.00    0.45    --  -86.25 -65.00 129.00   36
125  \w   -157.00-124.00   1.00    0.45    --  -86.25 -69.00 -47.64   33
126  \w   -100.00 -74.00   1.00    0.45    --  -86.25 -63.00 -70.16   26
127  \w   -104.00 -79.00   1.00    0.45    --  -86.25 -60.00 -91.38   25
128  \w    -97.00 -68.00   1.00    0.45    --  -86.25 -68.00-171.16   29
129  \w    -83.00 -57.00   1.00    0.45    --  -74.00 -67.00-178.37   26
;
_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      0.1291283000
_diffrn_orient_matrix_UB_12      -0.0832129000
_diffrn_orient_matrix_UB_13      -0.0982862000
_diffrn_orient_matrix_UB_21      -0.0847986000
_diffrn_orient_matrix_UB_22      -0.0428587000
_diffrn_orient_matrix_UB_23      -0.0285181000
_diffrn_orient_matrix_UB_31      -0.0142077000
_diffrn_orient_matrix_UB_32      0.1041292000
_diffrn_orient_matrix_UB_33      -0.0898949000
_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  0.0970
_diffrn_reflns_av_unetI/netI     0.0489
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            41062
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.068
_diffrn_reflns_theta_max         67.068
_diffrn_reflns_theta_min         3.909
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.717
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67546
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.112a (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    1.332
_exptl_crystal_description       block
_exptl_crystal_F_000             640
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Ethylacetate'
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.320
_refine_diff_density_min         -0.257
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     417
_refine_ls_number_reflns         5401
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0611
_refine_ls_R_factor_gt           0.0496
_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^)+(0.0547P)^2^+0.7152P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1226
_refine_ls_wR_factor_ref         0.1296
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4513
_reflns_number_total             5401
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02763a4.cif
_cod_data_source_block           220225a_auto
_cod_depositor_comments
'Adding full bibliography for 1571688--1571690.cif.'
_cod_original_cell_volume        1517.57(9)
_cod_database_code               1571690
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CO
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C12(H12), C28(H28)
2.b Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C24(H24A,H24B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C5(H5), C7(H7), C11(H11), C13(H13), C15(H15), C18(H18), C21(H21),
 C22(H22), C25(H25), C27(H27), C29(H29), C31(H31), C32(H32), C33(H33), C34(H34),
  C35(H35), C37(H37), C38(H38), C39(H39)
2.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C17(H17A,H17B,H17C)
;
_shelx_res_checksum              76284
_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 4.835
_oxdiff_exptl_absorpt_empirical_full_min 0.201