Formation of complex cyclic compounds <i>via</i> a dehydrogenative Diels-Alder reaction.
Xu, Zhongwei; Lei, Yu; Chang, Meng; Qiang, Ruihua; Hu, Qiong; Hu, Yimin; Organic & biomolecular chemistry 23 (2025) 9330–9335; doi:10.1039/d5ob01117e

data_7160740
_publ_section_title
;
 Formation of complex cyclic compounds <i>via</i> a dehydrogenative
 Diels-Alder reaction.
;
_journal_issue                   41
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              9330
_journal_page_last               9335
_journal_paper_doi               10.1039/d5ob01117e
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C45 H36 O4, C H2 Cl2'
_chemical_formula_sum            'C46 H38 Cl2 O4'
_chemical_formula_weight         725.66
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-11-15
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-06-26 deposited with the CCDC.	2025-09-15 downloaded from the CCDC.
;
_cell_angle_alpha                109.920(5)
_cell_angle_beta                 98.261(6)
_cell_angle_gamma                106.012(5)
_cell_formula_units_Z            2
_cell_length_a                   12.339(2)
_cell_length_b                   13.009(2)
_cell_length_c                   14.809(3)
_cell_measurement_reflns_used    9793
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      29.392
_cell_measurement_theta_min      2.624
_cell_volume                     2072.6(6)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Bruker D8 Venture diffractometer'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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_temperature      298(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.952
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0832
_diffrn_reflns_av_unetI/netI     0.0661
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            98259
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.291
_diffrn_reflns_theta_min         2.624
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.197
_exptl_absorpt_correction_T_max  0.7462
_exptl_absorpt_correction_T_min  0.6440
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0874 before and 0.0718 after correction.
The Ratio of minimum to maximum transmission is 0.8630.
The \l/2 correction factor is Not present.
;
_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    1.163
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             760
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.434
_refine_diff_density_min         -0.263
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     759
_refine_ls_number_reflns         12909
_refine_ls_number_restraints     983
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.1528
_refine_ls_R_factor_gt           0.0757
_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^)+(0.1178P)^2^+0.4250P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1989
_refine_ls_wR_factor_ref         0.2456
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6710
_reflns_number_total             12909
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01117e2.cif
_cod_data_source_block           20241115b
_cod_depositor_comments
'Adding full bibliography for 7160738--7160742.cif.'
_cod_original_cell_volume        2072.4(7)
_cod_database_code               7160740
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.977
_shelx_estimated_absorpt_t_min   0.971
_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. Restrained distances
 C46-Cl1 = C46-Cl2 = C46A-Cl1A = C46A-Cl2A = C46B-Cl1B = C46B-Cl2B = C46C-Cl1C
 = C46C-Cl2C
 1.79 with sigma of 0.01
 Cl1-Cl2 = Cl1A-Cl2A = Cl1B-Cl2B = Cl1C-Cl2C
 2.924 with sigma of 0.02
3. Restrained planarity
 O4A, C12, C1, O3A
 with sigma of 0.1
 C20, C18, C17, C21, C19, C16, C15
 with sigma of 0.1
 C32, C30, C29, C33, C31, C34, C28
 with sigma of 0.1
 C20A, C18A, C17A, C21A, C19A, C16, C15
 with sigma of 0.1
 C33A, C29, C30A, C32A, C34A, C31A, C28
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C9 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim
C43 \\sim C44 \\sim C45 \\sim C37A \\sim C38A \\sim C39A \\sim C40A \\sim C41A
\\sim C42A \\sim C43A \\sim C44A \\sim C45A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C12 \\sim C13 \\sim O3 \\sim O4 \\sim C13A \\sim O3A \\sim O4A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33 \\sim C34 \\sim C30A \\sim C31A
\\sim C32A \\sim C33A \\sim C34A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C46 \\sim Cl1 \\sim Cl2 \\sim C46A \\sim Cl1A \\sim Cl2A \\sim C46B \\sim Cl1B
\\sim Cl2B \\sim Cl1C \\sim C46C \\sim Cl2C: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C17A \\sim C18A
\\sim C19A \\sim C20A \\sim C21A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
5. Same fragment restrains
{C9, C36, C37A, C38A, C39A, C40A, C41A, C42A, C43A, C44A, C45A} sigma for 1-2:
0.01, 1-3: 0.01
as in
{C9, C36, C37, C38, C39, C40, C41, C42, C43, C44, C45}
{C12, C13A, O3A, O4A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{C12, C13, O3, O4}
{C16, C17A, C18A, C19A, C20A, C21A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{C16, C17, C18, C19, C20, C21}
{C29, C30A, C31A, C32A, C33A, C34A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{C29, C30, C31, C32, C33, C34}
6. Others
 1*[Sof(C46)+Sof(H46A)+Sof(H46B)+Sof(Cl1)+Sof(Cl2)]+1*[Sof(C46A)+Sof(H46C)+
 Sof(H46D)+Sof(Cl1A)+Sof(Cl2A)]+1*[Sof(C46B)+Sof(H46E)+Sof(H46F)+Sof(Cl1B)+
 Sof(Cl2B)]+1*[Sof(Cl1C)+Sof(C46C)+Sof(H46G)+Sof(H46H)+Sof(Cl2C)]=1 with esd of
 0
 Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(Cl1)=Sof(Cl2)=FVAR(1)
 Sof(C46A)=Sof(H46C)=Sof(H46D)=Sof(Cl1A)=Sof(Cl2A)=FVAR(2)
 Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(O3A)=Sof(O4A)=1-FVAR(3)
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(O3)=Sof(O4)=FVAR(3)
 Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=
 Sof(H20A)=Sof(C21A)=Sof(H21A)=1-FVAR(4)
 Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20)=
 Sof(C21)=Sof(H21)=FVAR(4)
 Sof(H9B)=Sof(H36A)=Sof(C37A)=Sof(H37A)=Sof(C38A)=Sof(H38A)=Sof(C39A)=
 Sof(H39C)=Sof(H39D)=Sof(C40A)=Sof(C41A)=Sof(H41A)=Sof(C42A)=Sof(H42A)=
 Sof(C43A)=Sof(C44A)=Sof(H44A)=Sof(C45A)=Sof(H45A)=1-FVAR(5)
 Sof(H9A)=Sof(H36)=Sof(C37)=Sof(H37)=Sof(C38)=Sof(H38)=Sof(C39)=Sof(H39A)=
 Sof(H39B)=Sof(C40)=Sof(C41)=Sof(H41)=Sof(C42)=Sof(H42)=Sof(C43)=Sof(C44)=
 Sof(H44)=Sof(C45)=Sof(H45)=FVAR(5)
 Sof(C30A)=Sof(H30A)=Sof(C31A)=Sof(H31A)=Sof(C32A)=Sof(H32A)=Sof(C33A)=
 Sof(H33A)=Sof(C34A)=Sof(H34A)=1-FVAR(6)
 Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31)=Sof(C32)=Sof(H32)=Sof(C33)=Sof(H33)=
 Sof(C34)=Sof(H34)=FVAR(6)
 Sof(C46B)=Sof(H46E)=Sof(H46F)=Sof(Cl1B)=Sof(Cl2B)=FVAR(7)
 Sof(Cl1C)=Sof(C46C)=Sof(H46G)=Sof(H46H)=Sof(Cl2C)=FVAR(8)
7.a Ternary CH refined with riding coordinates:
 C9(H9A), C9(H9B), C28(H28)
7.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C39(H39A,H39B), C39A(H39C,H39D), C46(H46A,H46B), C46A(H46C,H46D),
  C46B(H46E,H46F), C46C(H46G,H46H)
7.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C36(H36), C36(H36A), C37(H37), C38(H38), C41(H41), C42(H42), C44(H44),
  C45(H45), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C23(H23),
 C24(H24), C25(H25), C26(H26), C27(H27), C30(H30), C31(H31), C32(H32), C33(H33),
  C34(H34), C35(H35), C17A(H17A), C18A(H18A), C19A(H19A), C20A(H20A),
 C21A(H21A), C30A(H30A), C31A(H31A), C32A(H32A), C33A(H33A), C34A(H34A),
 C37A(H37A), C38A(H38A), C41A(H41A), C42A(H42A), C44A(H44A), C45A(H45A)
7.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C13A(H13D,H13E,H13F)
;
_shelx_res_checksum              80257
_olex2_submission_special_instructions 'No special instructions were received'