General access to furan-substituted <i>gem</i>-difluoroalkenes enabled by PFTB-promoted cross-coupling of ene-yne-ketones and difluorocarbene.
Li, Na; Li, Chenghui; Zhou, Qianying; Zhang, Xin; Deng, Zhouming; Jiang, Zhong-Xing; Yang, Zhigang; Chemical science 16 (2025) 1455–1464; doi:10.1039/d4sc08247h

data_1573543
_publ_section_title
;
 General access to furan-substituted <i>gem</i>-difluoroalkenes enabled by
 PFTB-promoted cross-coupling of ene-yne-ketones and difluorocarbene.
;
_journal_issue                   3
_journal_name_full               'Chemical science'
_journal_page_first              1455
_journal_page_last               1464
_journal_paper_doi               10.1039/d4sc08247h
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C27 H20 F2 O3'
_chemical_formula_sum            'C27 H20 F2 O3'
_chemical_formula_weight         430.43
_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             2024-05-21
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-05-21 deposited with the CCDC.	2024-12-17 downloaded from the CCDC.
;
_cell_angle_alpha                95.7908(14)
_cell_angle_beta                 99.8803(15)
_cell_angle_gamma                106.3386(16)
_cell_formula_units_Z            8
_cell_length_a                   9.86943(17)
_cell_length_b                   17.5275(3)
_cell_length_c                   26.1199(5)
_cell_measurement_reflns_used    30855
_cell_measurement_temperature    131(19)
_cell_measurement_theta_max      76.1790
_cell_measurement_theta_min      2.6190
_cell_volume                     4218.10(14)
_computing_cell_refinement       'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.105a 64-bit (release 11-01-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.105a (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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      131(19)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.980
_diffrn_measured_fraction_theta_max 0.980
_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   -104.00 -78.00   0.50    0.18    --  -64.08 -15.00 150.00   52
  2  \w    -88.00 -62.00   0.50    0.18    --  -64.08 -15.00   0.00   52
  3  \w    -95.00 -58.00   0.50    0.18    --  -64.08 -15.00 -30.00   74
  4  \w    -94.00 -58.00   0.50    0.18    --  -64.08 -15.00 -90.00   72
  5  \w   -103.00 -78.00   0.50    0.18    --  -64.08 -15.00-120.00   50
  6  \w   -104.00 -63.00   0.50    0.18    --  -64.08 -15.00-150.00   82
  7  \w   -117.00 -80.00   0.50    0.18    --  -77.00 -15.00-180.00   74
  8  \w   -105.00 -68.00   0.50    0.18    --  -72.27 -15.00-150.00   74
  9  \w   -112.00 -87.00   0.50    0.18    --  -77.00 -15.00-150.00   50
 10  \w   -110.00 -72.00   0.50    0.18    --  -77.00 -15.00 -90.00   76
 11  \w   -117.00 -80.00   0.50    0.18    --  -77.00 -15.00 -30.00   74
 12  \w   -116.00 -76.00   0.50    0.18    --  -77.00 -15.00  60.00   80
 13  \w   -115.00 -73.00   0.50    0.18    --  -77.00 -15.00 120.00   84
 14  \w     58.00  89.00   0.50    0.18    --   62.60  15.00-120.00   62
 15  \w     62.00 100.00   0.50    0.18    --   62.60  15.00-180.00   76
 16  \w     76.00 101.00   0.50    0.18    --   71.73  15.00-180.00   50
 17  \w     75.00 101.00   0.50    0.18    --   71.73  15.00-150.00   52
 18  \w     64.00 110.00   0.50    0.18    --   71.73  15.00 -30.00   92
 19  \w     70.00 100.00   0.50    0.18    --   76.23  15.00  90.00   60
 20  \w     77.00 105.00   0.50    0.18    --   71.73  15.00 120.00   56
 21  \w     55.00  98.00   0.50    0.18    --   62.60  15.00 120.00   86
 22  \w     40.00  66.00   0.50    0.18    --   62.60-125.00 150.00   52
 23  \w     35.00  66.00   0.50    0.18    --   71.73-125.00  90.00   62
 24  \w     67.00  92.00   0.50    0.18    --   76.23-125.00  30.00   50
 25  \w     46.00  72.00   0.50    0.18    --   71.73-125.00 -30.00   52
 26  \w     26.00  64.00   0.50    0.18    --   62.60-125.00 -90.00   76
 27  \w     49.00  87.00   0.50    0.18    --   71.73-125.00-120.00   76
 28  \w    -89.00 -64.00   0.50    0.18    --  -76.00 120.00-137.03   50
 29  \w   -102.00 -45.00   0.50    0.18    --  -77.15 139.00-112.68  114
 30  \w   -101.00 -65.00   0.50    0.18    --  -77.15 137.00 -76.34   72
 31  \w   -101.00 -45.00   0.50    0.18    --  -77.15 137.00 -56.24  112
 32  \w   -103.00 -71.00   0.50    0.18    --  -77.15 140.00  41.11   64
 33  \w    -99.00 -38.00   0.50    0.18    --  -76.00 136.00  35.84  122
 34  \w   -100.00 -67.00   0.50    0.18    --  -77.15 135.00 -35.09   66
 35  \w   -103.00 -50.00   0.50    0.18    --  -77.15 140.00  77.57  106
 36  \w    -98.00 -35.00   0.50    0.18    --  -72.00 140.00  74.74  126
 37  \w    -74.00 -49.00   0.50    0.18    --  -77.15 127.00 111.24   50
 38  \w    -69.00 -40.00   0.50    0.18    --  -77.15 135.00 148.39   58
 39  \w    -99.00 -38.00   0.50    0.18    --  -76.00 136.00 159.52  122
 40  \w   -100.00 -75.00   0.50    0.18    --  -77.15 135.00 148.39   50
 41  \w   -100.00 -67.00   0.50    0.18    --  -77.15 135.00 120.06   66
 42  \w    -94.00 -59.00   0.50    0.18    --  -77.15 126.00  29.76   70
 43  \w    -94.00 -44.00   0.50    0.18    --  -77.15 126.00   2.41  100
 44  \w    -79.00 -27.00   0.50    0.18    --  -64.08 125.00 -60.00  104
 45  \w    -88.00 -47.00   0.50    0.18    --  -72.27 125.00-120.00   82
 46  \w    -94.00 -51.00   0.50    0.18    --  -77.15 126.00-155.51   86
 47  \w    -87.00 -47.00   0.50    0.18    --  -72.27 125.00-180.00   80
 48  \w    -92.00 -58.00   0.50    0.18    --  -77.15 124.00-118.59   68
 49  \w    -87.00 -48.00   0.50    0.18    --  -72.27 125.00 -60.00   78
 50  \w    -88.00 -63.00   0.50    0.18    --  -72.27 125.00  30.00   50
 51  \w     55.00  79.50   0.50    0.18    --   62.74  15.00-150.00   49
 52  \w    -69.00 -43.00   0.50    0.18    --  -76.73 125.00-120.00   52
 53  \w   -112.00 -86.00   0.50    0.18    --  -76.73 -15.00   0.00   52
 54  \w    -97.00 -72.00   0.50    0.18    --  -81.53 125.00  60.00   50
 55  \w    -97.00 -72.00   0.50    0.18    --  -81.53 125.00-180.00   50
 56  \w    -97.00 -72.00   0.50    0.18    --  -81.53 125.00-120.00   50
 57  \w    -97.00 -72.00   0.50    0.18    --  -81.53 125.00 -60.00   50
 58  \w    -97.00 -56.00   0.50    0.18    --  -81.53 125.00 -90.00   82
 59  \w    -97.00 -72.00   0.50    0.18    --  -81.53 125.00 150.00   50
 60  \w    -97.00 -72.00   0.50    0.18    --  -81.53 125.00-150.00   50
 61  \w    -96.00 -46.00   0.50    0.18    --  -81.53 125.00  30.00  100
 62  \w    -97.00 -72.00   0.50    0.18    --  -81.53 125.00 -30.00   50
 63  \w    -97.00 -72.00   0.50    0.18    --  -81.53 125.00  90.00   50
 64  \w    -97.00 -64.00   0.50    0.18    --  -81.53 125.00   0.00   66
 65  \w    -97.00 -72.00   0.50    0.18    --  -81.53 125.00 120.00   50
 66  \w   -104.00 -79.00   0.50    0.18    --  -63.92 -15.00-150.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom 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      -0.0843062000
_diffrn_orient_matrix_UB_12      0.0182734000
_diffrn_orient_matrix_UB_13      -0.0501996000
_diffrn_orient_matrix_UB_21      -0.0519384000
_diffrn_orient_matrix_UB_22      -0.0901971000
_diffrn_orient_matrix_UB_23      -0.0232303000
_diffrn_orient_matrix_UB_31      -0.1335449000
_diffrn_orient_matrix_UB_32      -0.0116388000
_diffrn_orient_matrix_UB_33      0.0248596000
_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  0.1387
_diffrn_reflns_av_unetI/netI     0.0565
_diffrn_reflns_Laue_measured_fraction_full 0.980
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            63084
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        66.599
_diffrn_reflns_theta_max         66.599
_diffrn_reflns_theta_min         2.660
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.825
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82668
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.105a (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    1.356
_exptl_crystal_description       needle
_exptl_crystal_F_000             1792
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.656
_refine_diff_density_min         -0.708
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.128
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1203
_refine_ls_number_reflns         14603
_refine_ls_number_restraints     123
_refine_ls_restrained_S_all      1.150
_refine_ls_R_factor_all          0.0927
_refine_ls_R_factor_gt           0.0645
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1757P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2025
_refine_ls_wR_factor_ref         0.2588
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10576
_reflns_number_total             14603
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08247h2.cif
_cod_data_source_block           20240508-yzg2
_cod_depositor_comments          'Adding full bibliography for 1573543.cif.'
_cod_original_cell_volume        4218.11(13)
_cod_database_code               1573543
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         CHOF
_shelx_estimated_absorpt_t_max   0.968
_shelx_estimated_absorpt_t_min   0.922
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C14-C116 = C21-C116 = C52-C51 = C53-C51
 1.54 with sigma of 0.01
 C6A-C1 = C2A-C1 = C3A-C2A = C4-C3A = C5A-C4 = C6A-C5A
 1.39 with sigma of 0.001
 C6A-C11
 2.481 with sigma of 0.01
 C1-C4
 2.78 with sigma of 0.01
 C6A-C3A
 2.78 with sigma of 0.01
 C2A-C5A
 2.78 with sigma of 0.01
 C11-C2A
 2.481 with sigma of 0.001
 C11-C6A
 2.481 with sigma of 0.001
 C6A-C2A
 2.408 with sigma of 0.001
 C1-C2 \\sim C1-C2A
 with sigma of 0.02
 C4-C2 \\sim C4-C2A
 with sigma of 0.04
 C1-C6 \\sim C1-C6A
 with sigma of 0.02
 C4-C3 \\sim C4-C3A
 with sigma of 0.02
 C1-C3 \\sim C1-C3A
 with sigma of 0.04
 C4-C5 \\sim C4-C5A
 with sigma of 0.02
 C2-C3 \\sim C2A-C3A
 with sigma of 0.02
 C1-C5 \\sim C1-C5A
 with sigma of 0.04
 C4-C6 \\sim C4-C6A
 with sigma of 0.04
 C6-C5 \\sim C6A-C5A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C6) \\sim
Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C1) \\sim Ueq, Uanis(C6A) \\sim Ueq, Uanis(C5A) \\sim Ueq, Uanis(C4)
\\sim Ueq, Uanis(C3A) \\sim Ueq, Uanis(C2A) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C6A) \\sim Ueq, Uanis(C5A) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C3A)
\\sim Ueq, Uanis(C2A) \\sim Ueq, Uanis(C1) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 C1, C6, C5, C4, C3, C2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
5. Others
 Sof(H51c)=Sof(H51d)=Sof(H11c)=Sof(H11d)=Sof(C53)=Sof(H53a)=Sof(H53b)=
 Sof(H53c)=Sof(C21)=Sof(H21a)=Sof(H21b)=Sof(H21c)=1-FVAR(1)
 Sof(H51a)=Sof(H51b)=Sof(H11a)=Sof(H11b)=Sof(C52)=Sof(H52a)=Sof(H52b)=
 Sof(H52c)=Sof(C14)=Sof(H14a)=Sof(H14b)=Sof(H14c)=FVAR(1)
 Sof(C6A)=Sof(H6A)=Sof(C5A)=Sof(H5A)=Sof(C3A)=Sof(H3A)=Sof(C2A)=Sof(H2A)=
 Sof(H4b)=1-FVAR(2)
 Sof(C3)=Sof(H3)=Sof(C2)=Sof(H2)=Sof(C6)=Sof(H6)=Sof(C5)=Sof(H5)=Sof(H4a)=
 FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C25(H25a,H25b), C84(H84a,H84b), C51(H51a,H51b), C51(H51c,H51d), C116(H11c,
 H11d), C116(H11a,H11b)
6.b Aromatic/amide H refined with riding coordinates:
 C100(H100), C103(H103), C76(H76), C38(H38), C60(H60), C39(H39), C29(H29),
 C107(H107), C104(H104), C98(H98), C17(H17), C35(H35), C101(H101), C33(H33),
 C36(H36), C94(H94), C42(H42), C59(H59), C32(H32), C130(H130), C126(H126),
 C120(H120), C31(H31), C56(H56), C65(H65), C123(H123), C124(H124), C58(H58),
 C66(H66), C57(H57), C62(H62), C63(H63), C122(H122), C121(H121), C30(H30),
 C129(H129), C97(H97), C64(H64), C127(H127), C128(H128), C12(H12), C96(H96),
 C95(H95), C13(H13), C72(H72), C68(H68), C71(H71), C92(H92), C6A(H6A), C5A(H5A),
  C3A(H3A), C2A(H2A), C69(H69), C90(H90), C91(H91), C88(H88), C9(H9), C10(H10),
 C89(H89), C3(H3), C2(H2), C6(H6), C5(H5), C4(H4b), C4(H4a)
6.c Fitted hexagon refined as free rotating group:
 C3(C2,C1,C6,C5,C4)
6.d Idealised Me refined as rotating group:
 C85(H85a,H85b,H85c), C26(H26a,H26b,H26c), C52(H52a,H52b,H52c), C53(H53a,H53b,
 H53c), C21(H21a,H21b,H21c), C14(H14a,H14b,H14c)
;
_shelx_res_checksum              58390
_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 3.461
_oxdiff_exptl_absorpt_empirical_full_min 0.513