Carbene-organocatalyzed enantioselective [5+5] annulation of dienols and dienals towards tetrahydroisochromen-1-ones.
Xu, Ke; Zhao, Jiayi; Lin, Kejun; Zhu, Tingshun; Chemical communications (Cambridge, England) 61 (2025) 10602–10605; doi:10.1039/d5cc02347e

data_7134661
_publ_section_title
;
 Carbene-organocatalyzed enantioselective [5+5] annulation of dienols and
 dienals towards tetrahydroisochromen-1-ones.
;
_journal_issue                   57
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              10602
_journal_page_last               10605
_journal_paper_doi               10.1039/d5cc02347e
_journal_volume                  61
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C32 H29 N O7, 0.25(C6 H14)'
_chemical_formula_sum            'C35 H36 N O7'
_chemical_formula_weight         582.65
_space_group_crystal_system      tetragonal
_space_group_IT_number           78
_space_group_name_Hall           'P 4cw'
_space_group_name_H-M_alt        'P 43'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2020-12-13
_audit_creation_method
;
Olex2 1.3-beta
(compiled 2020.05.22 svn.r1d9e7f8d for OlexSys, GUI svn.r6115)
;
_audit_update_record
;
2024-08-14 deposited with the CCDC.	2025-06-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.7397(3)
_cell_length_b                   16.7397(3)
_cell_length_c                   10.5216(3)
_cell_measurement_reflns_used    10197
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      76.0090
_cell_measurement_theta_min      4.9220
_cell_volume                     2948.34(11)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2913
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.987
_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   -129.00  47.00   1.00    4.00    --  -41.14   0.00-120.00  176
  2  \w   -114.00 -13.00   1.00    4.00    --  -41.14 -57.00-150.00  101
  3  \w     17.00  69.00   1.00    4.00    --   41.14  37.00-150.00   52
  4  \w     31.00  56.00   1.00    4.00    --   41.14  77.00-120.00   25
  5  \w     35.00  73.00   1.00    4.00    --   41.14-125.00 -30.00   38
  6  \w     79.00 105.00   1.00   16.00    --  112.00  77.00-180.00   26
  7  \w    140.00 167.00   1.00   16.00    --  112.00  61.00-120.00   27
  8  \w     83.00 110.00   1.00   16.00    --  112.00  61.00-150.00   27
  9  \w    130.00 178.00   1.00   16.00    --  112.00  77.00-150.00   48
 10  \w     80.00 105.00   1.00   16.00    --  112.00  77.00-150.00   25
 11  \w     61.00  88.00   1.00   16.00    --  112.00  15.00 -60.00   27
 12  \w     86.00 112.00   1.00   16.00    --  112.00  45.00-120.00   26
 13  \w     79.00 106.00   1.00   16.00    --  112.00  77.00-120.00   27
 14  \w     87.00 113.00   1.00   16.00    --  112.00  45.00-150.00   26
 15  \w     83.00 109.00   1.00   16.00    --  112.00  61.00-120.00   26
 16  \w    114.00 176.00   1.00   16.00    --  112.00  61.00 -90.00   62
 17  \w     83.00 110.00   1.00   16.00    --  112.00  61.00 -90.00   27
 18  \w     85.00 110.00   1.00   16.00    --  112.00  30.00-120.00   25
 19  \w    140.00 175.00   1.00   16.00    --  112.00  77.00-180.00   35
 20  \w     87.00 114.00   1.00   16.00    --  112.00  45.00 -90.00   27
 21  \w     85.00 115.00   1.00   16.00    --  112.00  30.00 -90.00   30
 22  \w     91.00 118.00   1.00   16.00    --  112.00  61.00-180.00   27
 23  \w     39.00 114.00   1.00   16.00    --  112.00-125.00-150.00   75
 24  \w    124.00 178.00   1.00   16.00    --  112.00 125.00-120.00   54
 25  \w    -46.00 -20.00   1.00    4.00    --  -41.14 -77.00-180.00   26
 26  \w    -95.00 -69.00   1.00    4.00    --  -41.14 -37.00-180.00   26
 27  \w    -57.00 -31.00   1.00    4.00    --  -41.14 -77.00 120.00   26
 28  \w     82.00 107.00   1.00   16.00    --  111.37  61.00-150.00   25
 29  \w     86.00 112.00   1.00   16.00    --  111.37  45.00-150.00   26
 30  \w     79.00 105.00   1.00   16.00    --  111.37  77.00-150.00   26
 31  \w     82.00 108.00   1.00   16.00    --  111.37  61.00-120.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0884193000
_diffrn_orient_matrix_UB_12      0.0145589000
_diffrn_orient_matrix_UB_13      -0.0336323000
_diffrn_orient_matrix_UB_21      -0.0080277000
_diffrn_orient_matrix_UB_22      -0.0876990000
_diffrn_orient_matrix_UB_23      -0.0426756000
_diffrn_orient_matrix_UB_31      -0.0242004000
_diffrn_orient_matrix_UB_32      -0.0237366000
_diffrn_orient_matrix_UB_33      0.1360087000
_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  0.0265
_diffrn_reflns_av_unetI/netI     0.0251
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            20352
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.951
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.156
_diffrn_reflns_theta_min         3.734
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.742
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61060
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.313
_exptl_crystal_description       plate
_exptl_crystal_F_000             1236
_exptl_crystal_size_max          0.220
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.080
_refine_diff_density_max         0.796
_refine_diff_density_min         -0.363
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Flack x determined using 2204 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(2)
_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     539
_refine_ls_number_reflns         5846
_refine_ls_number_restraints     60
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0749
_refine_ls_R_factor_gt           0.0710
_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^)+(0.1623P)^2^+0.5334P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2088
_refine_ls_wR_factor_ref         0.2159
_reflns_Friedel_coverage         0.825
_reflns_Friedel_fraction_full    0.948
_reflns_Friedel_fraction_max     0.912
_reflns_number_gt                5412
_reflns_number_total             5846
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc02347e2.cif
_cod_data_source_block           2011a1320
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_absolute_configuration' value 'AD' was changed
to 'ad' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 7134660--7134669.cif.
;
_cod_original_cell_volume        2948.33(12)
_cod_database_code               7134661
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C35H32O7N
_chemical_oxdiff_usercomment     FCK5PC17-D1
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.854
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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. Shared sites
{N1, N1'}
{C3, C3'}
3. Restrained distances
 C33'-C34' = C34'-C35' = C35'-C36' = C36'-C37' = C37'-C38'
 1.48 with sigma of 0.005
 C33'-C35' = C34'-C36' = C35'-C37' = C36'-C38'
 2.5 with sigma of 0.01
 C33-C35 = C34-C36 = C35-C37 = C36-C38
 2.5 with sigma of 0.01
 C33-C34 = C34-C35 = C35-C36 = C36-C37 = C37-C38
 1.48 with sigma of 0.005
 N1-C24 \\sim N1-C26 \\sim N1'-C24 \\sim N1'-C26
 with sigma of 0.02
 C25-N1 \\sim C25-N1'
 with sigma of 0.02
 O6-O7 \\sim O6'-O7'
 with sigma of 0.02
 O6-N1 \\sim O7-N1 \\sim O6'-N1' \\sim O7'-N1'
 with sigma of 0.02
 O5-C30 \\sim O5'-C30'
 with sigma of 0.02
 C15-O5 \\sim C15'-O5'
 with sigma of 0.02
4. Restrained planarity
 C25, N1, O6, O7
 with sigma of 0.1
5. Rigid bond restraints
 C33, C34, C35, C36, C37, C38, C33', C34', C35', C36', C37', C38'
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C25, N1', O6', O7'
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C25, N1, O6, O7
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C3, C12, C13, C14, C15, C16, C17, O5, C30
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C3', C12', C13', C14', C15', C16', C17', O5', C30'
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
6. Uiso/Uaniso restraints and constraints
C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C33' \\sim C34'
\\sim C35' \\sim C36' \\sim C37' \\sim C38': within 2A with sigma of 0.002 and
sigma for terminal atoms of 0.004 within 2A
C25 \\sim N1' \\sim O6' \\sim O7': within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
C25 \\sim N1 \\sim O6 \\sim O7: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
C3 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim O5 \\sim
C30: within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01 within
2A
C3' \\sim C12' \\sim C13' \\sim C14' \\sim C15' \\sim C16' \\sim C17' \\sim O5'
\\sim C30': within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
within 2A
Uanis(C33) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C36)
\\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C33') \\sim Ueq,
Uanis(C34') \\sim Ueq, Uanis(C35') \\sim Ueq, Uanis(C36') \\sim Ueq,
Uanis(C37') \\sim Ueq, Uanis(C38') \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
Uanis(C25) \\sim Ueq, Uanis(N1') \\sim Ueq, Uanis(O6') \\sim Ueq, Uanis(O7')
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C25) \\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(O6) \\sim Ueq, Uanis(O7) \\sim
Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C3) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C14)
\\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C17) \\sim Ueq,
Uanis(O5) \\sim Ueq, Uanis(C30) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C3') \\sim Ueq, Uanis(C12') \\sim Ueq, Uanis(C13') \\sim Ueq, Uanis(C14')
\\sim Ueq, Uanis(C15') \\sim Ueq, Uanis(C16') \\sim Ueq, Uanis(C17') \\sim Ueq,
Uanis(O5') \\sim Ueq, Uanis(C30') \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(N1) = Uanis(N1')
Uanis(C3) = Uanis(C3')
7. Others
 Sof(C3')=Sof(C12')=Sof(C13')=Sof(H13')=Sof(C14')=Sof(H14')=Sof(C15')=
 Sof(C16')=Sof(H16')=Sof(C17')=Sof(H17')=Sof(O5')=Sof(C30')=Sof(H30D)=Sof(H30E)=
 Sof(H30F)=1-FVAR(1)
 Sof(C3)=Sof(C12)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(H14)=Sof(C15)=Sof(C16)=
 Sof(H16)=Sof(C17)=Sof(H17)=Sof(O5)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=
 FVAR(1)
 Sof(N1')=Sof(O6')=Sof(O7')=1-FVAR(2)
 Sof(N1)=Sof(O6)=Sof(O7)=FVAR(2)
 Fixed Sof: C33(0.25) H33A(0.25) H33B(0.25) H33C(0.25) C34(0.25) H34A(0.25)
 H34B(0.25) C35(0.25) H35A(0.25) H35B(0.25) C36(0.25) H36A(0.25) H36B(0.25)
 C37(0.25) H37A(0.25) H37B(0.25) C38(0.25) H38A(0.25) H38B(0.25) H38C(0.25)
 C33'(0.25) H33D(0.25) H33E(0.25) H33F(0.25) C34'(0.25) H34C(0.25) H34D(0.25)
 C35'(0.25) H35C(0.25) H35D(0.25) C36'(0.25) H36C(0.25) H36D(0.25) C37'(0.25)
 H37C(0.25) H37D(0.25) C38'(0.25) H38D(0.25) H38E(0.25) H38F(0.25)
8.a Riding coordinates:
 C30(H30A,H30B,H30C), C33(H33A,H33B,H33C), C36(H36A,H36B), C38(H38A,H38B,H38C),
  C30'(H30D,H30E,H30F), C33'(H33D,H33E,H33F), C36'(H36C,H36D), C38'(H38D,H38E,
 H38F), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23)
8.b Ternary CH refined with riding coordinates:
 C2(H2), C5(H5), C6(H6), C7(H7)
8.c Secondary CH2 refined with riding coordinates:
 C34(H34A,H34B), C35(H35A,H35B), C37(H37A,H37B), C34'(H34C,H34D), C35'(H35C,
 H35D), C37'(H37C,H37D), C31(H31A,H31B)
8.d Aromatic/amide H refined with riding coordinates:
 C13(H13), C14(H14), C16(H16), C17(H17), C13'(H13'), C14'(H14'), C16'(H16'),
 C17'(H17'), C4(H4), C26(H26), C27(H27), C28(H28), C29(H29)
8.e Fitted hexagon refined as free rotating group:
 C12(C13,C14,C15,C16,C17), C12'(C13',C14',C15',C16',C17')
8.f Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C32(H32A,H32B,H32C)
;
_shelx_res_checksum              4132
_shelx_hkl_checksum              29286
_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 1.620
_oxdiff_exptl_absorpt_empirical_full_min 0.618