Asymmetric total synthesis of penicilfuranone A through an NHC-catalyzed umpolung strategy
Ding, Yiming; Long, Xianwen; Zhang, Jingwei; Qu, Chunlei; Wang, Peng; Yang, Xiaodong; Puno, Pema-Tenzin; Deng, Jun; Chemical Science 16 (2025) 8302–8308; doi:10.1039/D5SC01508A

data_1574363
_publ_section_title
;
 Asymmetric total synthesis of penicilfuranone A through an NHC-catalyzed
 umpolung strategy
;
_journal_issue                   19
_journal_name_full               'Chemical Science'
_journal_page_first              8302
_journal_page_last               8308
_journal_paper_doi               10.1039/D5SC01508A
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C21 H24 O6'
_chemical_formula_sum            'C21 H24 O6'
_chemical_formula_weight         372.40
_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
_audit_creation_date             2025-02-20
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-02-20 deposited with the CCDC.	2025-04-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.4910(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.75710(10)
_cell_length_b                   19.7605(2)
_cell_length_c                   11.26570(10)
_cell_measurement_reflns_used    25543
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.0610
_cell_measurement_theta_min      2.3320
_cell_volume                     1878.65(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.978
_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    -53.00 -23.00   0.50    0.05    --  -77.88  64.00-180.00   60
  2  \w    -30.00  -5.00   0.50    0.05    --  -53.69  71.00 -82.00   50
  3  \w    -62.00 -37.00   0.50    0.05    --  -61.31  71.00 -82.00   50
  4  \w    -49.00 -23.00   0.50    0.05    --  -77.88  64.00-150.00   52
  5  \w    -60.00 -35.00   0.50    0.05    --  -77.88  71.00 -82.00   50
  6  \w    -30.00  -3.00   0.50    0.05    --  -61.31  45.00-150.00   54
  7  \w    -55.00 -29.00   0.50    0.05    --  -77.88  64.00 -30.00   52
  8  \w    -55.00 -27.00   0.50    0.05    --  -77.88  64.00  30.00   56
  9  \w    -48.00 -22.00   0.50    0.05    --  -77.88  64.00  90.00   52
 10  \w    -31.00   0.00   0.50    0.05    --  -61.31  45.00  60.00   62
 11  \w    -27.00  -1.00   0.50    0.05    --  -61.31  45.00  30.00   52
 12  \w    -29.00  -1.00   0.50    0.05    --  -61.31  45.00 -30.00   56
 13  \w    -29.00  -4.00   0.50    0.05    --  -61.31  45.00 -90.00   50
 14  \w    -31.00  -2.00   0.50    0.05    --  -61.31  45.00-120.00   58
 15  \w     36.00  61.00   0.50    0.05    --   93.94-112.00 -90.00   50
 16  \w     36.00  61.00   0.50    0.05    --   93.94-112.00-150.00   50
 17  \w     36.00  61.00   0.50    0.05    --   93.94-112.00-120.00   50
 18  \w     40.00  88.00   0.50    0.05    --   98.00-101.00 -98.15   96
 19  \w     36.00  61.00   0.50    0.05    --   93.94-112.00   0.00   50
 20  \w     38.00  73.00   0.50    0.05    --   93.94-112.00  60.00   70
 21  \w     52.00  78.00   0.50    0.05    --   93.94-112.00  90.00   52
 22  \w     41.00  78.00   0.50    0.05    --   93.94 -92.00 120.00   74
 23  \w     41.00  87.00   0.50    0.05    --   98.00 -99.00  89.86   92
 24  \w     40.00  65.00   0.50    0.05    --   93.94 -92.00  60.00   50
 25  \w     40.00  65.00   0.50    0.05    --   93.94 -92.00   0.00   50
 26  \w     62.00  88.00   0.50    0.05    --   93.94 -92.00 -30.00   52
 27  \w     43.00  83.00   0.50    0.05    --   93.94 -92.00 -90.00   80
 28  \w     41.00  84.00   0.50    0.05    --   93.94 -92.00-180.00   86
 29  \w     45.00  84.00   0.50    0.05    --   98.00 -91.00-155.27   78
 30  \w     57.00  93.00   0.50    0.05    --   93.94 -92.00 150.00   72
 31  \w     45.00  70.00   0.50    0.05    --   93.94 -77.00 120.00   50
 32  \w     44.00  69.00   0.50    0.05    --   93.94 -77.00  90.00   50
 33  \w     13.00  38.00   0.50    0.05    --   51.80 -71.00 146.00   50
 34  \w      9.00  35.00   0.50    0.05    --   57.70 -71.00 146.00   52
 35  \w     44.00  69.00   0.50    0.05    --   93.94 -77.00 -30.00   50
 36  \w     45.00  70.00   0.50    0.05    --   93.94 -77.00-150.00   50
 37  \w      2.00  27.00   0.50    0.05    --   57.70 -61.00-150.00   50
 38  \w    119.00 152.00   0.50    0.05    --   93.94 112.00  30.00   66
 39  \w    104.00 130.00   0.50    0.05    --   93.94 112.00   0.00   52
 40  \w    106.00 132.00   0.50    0.05    --   93.94 112.00 -30.00   52
 41  \w    116.00 145.00   0.50    0.05    --   93.94 112.00 -60.00   58
 42  \w    117.00 145.00   0.50    0.05    --   93.94 112.00-120.00   56
 43  \w    117.00 143.00   0.50    0.05    --   93.94 112.00-180.00   52
 44  \w    104.00 130.00   0.50    0.05    --   93.94  77.00-120.00   52
 45  \w    114.00 143.00   0.50    0.05    --   93.94  77.00-180.00   58
 46  \w    116.00 142.00   0.50    0.05    --   93.94  77.00 -90.00   52
 47  \w    101.00 144.00   0.50    0.05    --   93.94  77.00 -30.00   86
 48  \w    118.00 144.00   0.50    0.05    --   93.94  77.00  30.00   52
 49  \w    117.00 144.00   0.50    0.05    --   93.94  77.00  60.00   54
 50  \w    109.00 135.00   0.50    0.05    --   93.94  77.00  90.00   52
 51  \w    101.00 141.00   0.50    0.05    --   93.94  77.00 120.00   80
 52  \w      9.00  34.00   0.50    0.05    --   14.00  68.00  24.23   50
 53  \w     90.00 116.00   0.50    0.05    --   93.94  64.00 120.00   52
 54  \w     91.00 116.00   0.50    0.05    --   93.94  64.00   0.00   50
 55  \w    124.00 149.00   0.50    0.05    --   93.94  64.00  30.00   50
 56  \w    124.00 149.00   0.50    0.05    --   93.94  64.00   0.00   50
 57  \w     93.00 120.00   0.50    0.05    --   93.94  64.00  60.00   54
 58  \w     90.00 116.00   0.50    0.05    --   93.94  64.00  30.00   52
 59  \w     99.00 124.00   0.50    0.05    --   93.94  71.00 -82.00   50
 60  \w     94.00 124.00   0.50    0.05    --   93.94  64.00-120.00   60
 61  \w     91.00 120.00   0.50    0.05    --   93.94  64.00-150.00   58
 62  \w     94.00 125.00   0.50    0.05    --   93.94  50.00-120.00   62
 63  \w     90.00 115.00   0.50    0.05    --   93.94  38.00-150.00   50
 64  \w    100.00 134.00   0.50    0.05    --   93.94  64.00 -90.00   68
 65  \w    131.00 156.00   0.50    0.05    --   93.94  25.00   0.00   50
 66  \w    132.00 157.00   0.50    0.05    --   93.94  25.00  60.00   50
 67  \w     49.00 154.00   0.50    0.05    --   98.00  23.00 102.09  210
 68  \w     94.00 119.00   0.50    0.05    --   93.94  50.00  60.00   50
 69  \w     80.00 119.00   0.50    0.05    --   93.94  25.00   0.00   78
 70  \w    130.00 155.00   0.50    0.05    --   93.94  12.00 -90.00   50
 71  \w    112.00 156.00   0.50    0.05    --   93.94  25.00-120.00   88
 72  \w     69.00  95.00   0.50    0.05    --   93.94  12.00 -90.00   52
 73  \w     20.00  45.00   0.50    0.05    --   22.00  63.00 -37.50   50
 74  \w     74.00 117.00   0.50    0.05    --   93.94  12.00  60.00   86
 75  \w    -61.00 -26.00   0.50    0.05    --  -26.00 -60.00  36.71   70
 76  \w    -62.00 -36.00   0.50    0.05    --  -38.00 -59.00   4.14   52
 77  \w   -113.00 -73.00   0.50    0.05    --  -70.00 -53.00  16.16   80
 78  \w   -125.00 -71.00   0.50    0.05    --  -66.00 -53.00 -99.58  108
 79  \w   -103.00 -73.00   0.50    0.05    --  -62.00 -53.00-179.03   60
 80  \w   -124.00 -88.00   0.50    0.05    --  -66.00 -50.00-153.20   72
 81  \w   -136.00 -87.00   0.50    0.05    --  -82.00 -50.00  -2.50   98
 82  \w   -139.00 -75.00   0.50    0.05    --  -77.88 -38.00  90.00  128
 83  \w   -139.00 -96.00   0.50    0.05    --  -82.00 -48.00 162.42   86
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0503655000
_diffrn_orient_matrix_UB_12      -0.0526386000
_diffrn_orient_matrix_UB_13      -0.0829948000
_diffrn_orient_matrix_UB_21      0.1122357000
_diffrn_orient_matrix_UB_22      -0.0329986000
_diffrn_orient_matrix_UB_23      0.1143933000
_diffrn_orient_matrix_UB_31      -0.1348764000
_diffrn_orient_matrix_UB_32      -0.0470682000
_diffrn_orient_matrix_UB_33      0.0129639000
_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     0.0136
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            31260
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.925
_diffrn_reflns_theta_min         4.475
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.794
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79664
_exptl_absorpt_correction_type   psi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.136a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dull light colourless'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.317
_exptl_crystal_description       needle
_exptl_crystal_F_000             792
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.577
_refine_diff_density_min         -0.243
_refine_diff_density_rms         0.048
_refine_ls_extinction_coef       0.0035(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     251
_refine_ls_number_reflns         3830
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0446
_refine_ls_R_factor_gt           0.0442
_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^)+(0.0432P)^2^+1.5106P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1075
_refine_ls_wR_factor_ref         0.1078
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3771
_reflns_number_total             3830
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01508a2.cif
_cod_data_source_block           37-mr-20250216a_auto
_cod_depositor_comments
'Adding full bibliography for 1574363--1574365.cif.'
_cod_database_code               1574363
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.857
_shelx_estimated_absorpt_t_min   0.797
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C009(H009), C00E(H00E)
2.b Secondary CH2 refined with riding coordinates:
 C00L(H00D,H00F)
2.c Aromatic/amide H refined with riding coordinates:
 C00H(H00H), C00I(H00I), C00M(H00M), C00N(H00N)
2.d Idealised Me refined as rotating group:
 C00K(H00A,H00B,H00C), C00O(H00G,H00J,H00K), C00P(H00L,H00O,H00P), C00Q(H00Q,
 H00R,H00S), C00R(H00T,H00U,H00V)
2.e Idealised tetrahedral OH refined as rotating group:
 O004(H004)
;
_shelx_res_checksum              75479
_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 1.722
_oxdiff_exptl_absorpt_empirical_full_min 0.505