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_1574364
_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
;
2025-03-24 deposited with the CCDC.	2025-04-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.1030(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.70700(10)
_cell_length_b                   19.1093(2)
_cell_length_c                   11.79410(10)
_cell_measurement_reflns_used    24420
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.9450
_cell_measurement_theta_min      4.3990
_cell_volume                     1961.04(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 0.976
_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     97.00 151.00   0.50    0.05    --   93.94 112.00  30.00  108
  2  \w     96.00 141.00   0.50    0.05    --   93.94 112.00 -30.00   90
  3  \w     24.00  51.00   0.50    0.05    --   26.00  62.00  13.38   54
  4  \w     15.00  40.00   0.50    0.05    --   18.00  67.00  47.02   50
  5  \w     23.00  48.00   0.50    0.05    --   26.00  62.00 127.68   50
  6  \w    120.00 147.00   0.50    0.05    --   93.94 112.00 120.00   54
  7  \w    125.00 151.00   0.50    0.05    --   93.94 112.00   0.00   52
  8  \w    111.00 145.00   0.50    0.05    --   93.94 112.00 -60.00   68
  9  \w    100.00 125.00   0.50    0.05    --   93.94  93.00 -91.00   50
 10  \w    113.00 152.00   0.50    0.05    --   93.94 112.00-180.00   78
 11  \w    118.00 143.00   0.50    0.05    --   93.94  77.00-120.00   50
 12  \w     91.00 117.00   0.50    0.05    --   93.94  64.00-120.00   52
 13  \w    100.00 137.00   0.50    0.05    --   93.94  77.00   0.00   74
 14  \w    105.00 146.00   0.50    0.05    --   93.94  64.00 -30.00   82
 15  \w    105.00 141.00   0.50    0.05    --   93.94  77.00 -30.00   72
 16  \w    112.00 148.00   0.50    0.05    --   93.94  64.00 -90.00   72
 17  \w     92.00 130.00   0.50    0.05    --   93.94  64.00-150.00   76
 18  \w     93.00 127.00   0.50    0.05    --   93.94  50.00 -30.00   68
 19  \w    111.00 138.00   0.50    0.05    --   93.94  77.00  30.00   54
 20  \w     91.00 129.00   0.50    0.05    --   93.94  64.00 120.00   76
 21  \w    110.00 135.00   0.50    0.05    --   93.94  77.00 150.00   50
 22  \w    112.00 137.00   0.50    0.05    --   93.94  50.00 150.00   50
 23  \w    117.00 150.00   0.50    0.05    --   93.94  50.00  30.00   66
 24  \w    109.00 135.00   0.50    0.05    --   93.94  38.00   0.00   52
 25  \w    108.00 155.00   0.50    0.05    --   93.94  25.00  30.00   94
 26  \w     95.00 144.00   0.50    0.05    --   93.94  50.00-120.00   98
 27  \w     99.00 131.00   0.50    0.05    --   93.94  50.00-180.00   64
 28  \w     98.00 136.00   0.50    0.05    --   93.94  50.00-150.00   76
 29  \w     82.00 114.00   0.50    0.05    --   98.00  22.00  -6.42   64
 30  \w     53.00  79.00   0.50    0.05    --   98.00  22.00  -6.42   52
 31  \w    116.00 143.00   0.50    0.05    --   98.00  24.00 164.81   54
 32  \w     49.00  97.00   0.50    0.05    --   98.00  24.00 164.81   96
 33  \w     46.00  72.00   0.50    0.05    --   93.94 -77.00  30.00   52
 34  \w     44.00  69.00   0.50    0.05    --   93.94 -77.00 120.00   50
 35  \w     44.00  69.00   0.50    0.05    --   93.94 -77.00   0.00   50
 36  \w     44.00  69.00   0.50    0.05    --   93.94 -77.00-120.00   50
 37  \w     55.00  92.00   0.50    0.05    --   93.94 -92.00-120.00   74
 38  \w     42.00  70.00   0.50    0.05    --   93.94-112.00-150.00   56
 39  \w     37.00  88.00   0.50    0.05    --   93.94-112.00 -30.00  102
 40  \w     42.00  91.00   0.50    0.05    --   98.00-101.00-128.18   98
 41  \w     39.00  65.00   0.50    0.05    --   93.94-112.00-180.00   52
 42  \w     64.00  90.00   0.50    0.05    --   98.00 -96.00 -32.50   52
 43  \w     36.00  61.00   0.50    0.05    --   93.94-112.00   0.00   50
 44  \w     59.00  85.00   0.50    0.05    --   93.94-112.00  90.00   52
 45  \w     51.00  77.00   0.50    0.05    --   93.94-112.00 150.00   52
 46  \w     41.00  66.00   0.50    0.05    --   93.94 -93.00 156.00   50
 47  \w     67.00  93.00   0.50    0.05    --   93.94 -92.00 120.00   52
 48  \w     41.00  91.00   0.50    0.05    --   93.94 -92.00  90.00  100
 49  \w     10.00  35.00   0.50    0.05    --   51.80 -93.00 156.00   50
 50  \w     16.00  41.00   0.50    0.05    --   57.70 -93.00 156.00   50
 51  \w     58.00  91.00   0.50    0.05    --   93.94 -92.00 -60.00   66
 52  \w     42.00  90.00   0.50    0.05    --   93.94 -92.00-180.00   96
 53  \w     66.00  92.00   0.50    0.05    --   93.94 -92.00-150.00   52
 54  \w     40.00  91.00   0.50    0.05    --   93.94 -92.00 -90.00  102
 55  \w     44.00  89.00   0.50    0.05    --   98.00 -92.00 -26.14   90
 56  \w     67.00  93.00   0.50    0.05    --   93.94 -92.00 150.00   52
 57  \w    -86.00 -29.00   0.50    0.05    --  -77.88 -12.00 -60.00  114
 58  \w    -89.00 -64.00   0.50    0.05    --  -62.00 -54.00-170.48   50
 59  \w   -119.00 -94.00   0.50    0.05    --  -62.00 -54.00-170.48   50
 60  \w   -114.00 -88.00   0.50    0.05    --  -82.00 -58.00-170.63   52
 61  \w   -110.00 -84.00   0.50    0.05    --  -82.00 -54.00-162.55   52
 62  \w   -113.00 -87.00   0.50    0.05    --  -82.00 -52.00-171.23   52
 63  \w   -132.00 -74.00   0.50    0.05    --  -74.00 -53.00  80.47  116
 64  \w   -107.00 -66.00   0.50    0.05    --  -66.00 -53.00  95.71   82
 65  \w    -99.00 -70.00   0.50    0.05    --  -70.00 -53.00 174.02   58
 66  \w   -132.00 -83.00   0.50    0.05    --  -77.88 -50.00 150.00   98
 67  \w   -106.00 -81.00   0.50    0.05    --  -82.00 -47.00  36.89   50
 68  \w   -124.00 -73.00   0.50    0.05    --  -74.00 -50.00 -64.27  102
 69  \w   -103.00 -77.00   0.50    0.05    --  -78.00 -48.00-167.71   52
 70  \w    -32.00  -7.00   0.50    0.05    --  -61.31  45.00-120.00   50
 71  \w    -53.00 -26.00   0.50    0.05    --  -77.88  64.00-150.00   54
 72  \w    -50.00 -25.00   0.50    0.05    --  -77.88  64.00 -90.00   50
 73  \w    -51.00 -25.00   0.50    0.05    --  -77.88  64.00-120.00   52
 74  \w    -75.00 -28.00   0.50    0.05    --  -77.88  77.00 -30.00   94
 75  \w    -54.00 -28.00   0.50    0.05    --  -77.88  64.00  30.00   52
 76  \w    -55.00 -28.00   0.50    0.05    --  -77.88  64.00  90.00   54
 77  \w    -48.00 -22.00   0.50    0.05    --  -77.88  64.00  60.00   52
 78  \w    -32.00  -6.00   0.50    0.05    --  -61.31  45.00   0.00   52
 79  \w    -36.00  -5.00   0.50    0.05    --  -61.31  61.00-120.00   62
 80  \w    -61.00 -36.00   0.50    0.05    --  -53.69  93.00 -91.00   50
 81  \w    -59.00 -34.00   0.50    0.05    --  -61.31  93.00 -91.00   50
 82  \w    -82.00 -57.00   0.50    0.05    --  -77.88  93.00 -91.00   50
 83  \w    -99.00 -33.00   0.50    0.05    --  -61.31 125.00 120.00  132
;
_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      -0.0212300000
_diffrn_orient_matrix_UB_12      0.0624506000
_diffrn_orient_matrix_UB_13      0.0805765000
_diffrn_orient_matrix_UB_21      0.1270220000
_diffrn_orient_matrix_UB_22      0.0403229000
_diffrn_orient_matrix_UB_23      -0.0598703000
_diffrn_orient_matrix_UB_31      -0.1214448000
_diffrn_orient_matrix_UB_32      0.0311700000
_diffrn_orient_matrix_UB_33      -0.0837888000
_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  0.0343
_diffrn_reflns_av_unetI/netI     0.0171
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            35739
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.183
_diffrn_reflns_theta_min         4.408
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.760
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70030
_exptl_absorpt_correction_type   multi-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            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.261
_exptl_crystal_description       needle
_exptl_crystal_F_000             792
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.236
_refine_diff_density_min         -0.312
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     250
_refine_ls_number_reflns         4002
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0374
_refine_ls_R_factor_gt           0.0359
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0485P)^2^+0.7087P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0934
_refine_ls_wR_factor_ref         0.0947
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3793
_reflns_number_total             4002
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01508a2.cif
_cod_data_source_block           37-mr-20250220a_auto
_cod_depositor_comments
'Adding full bibliography for 1574363--1574365.cif.'
_cod_database_code               1574364
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.928
_shelx_estimated_absorpt_t_min   0.804
_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:
 C00C(H00C), C00I(H00I)
2.b Secondary CH2 refined with riding coordinates:
 C00Q(H00S,H00T)
2.c Aromatic/amide H refined with riding coordinates:
 C00H(H00H), C00L(H00L), C00N(H00N), C00P(H00R)
2.d Idealised Me refined as rotating group:
 C00J(H00A,H00B,H00D), C00K(H00E,H00F,H00G), C00M(H00J,H00K,H00M), C00O(H00O,
 H00P,H00Q), C00R(H00U,H00V,H00W)
2.e Idealised tetrahedral OH refined as rotating group:
 O003(H003)
;
_shelx_res_checksum              7534
_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 1.951
_oxdiff_exptl_absorpt_empirical_full_min 0.605