Controlled gold-catalyzed 5-<i>exo-dig</i> cyclization of 3-sulfur-substituted 1,3-dien-5-ynes for synthesizing fulvenes and the <i>in situ</i> reaction with indoles.
Martínez-Núñez, Clara; Arribas-Torrecilla, Carlos; Sanz, Roberto; Suárez-Pantiga, Samuel; Chemical communications (Cambridge, England) 62 (2026) 2287–2291; doi:10.1039/d5cc06478c

data_7135536
_publ_section_title
;
 Controlled gold-catalyzed 5-<i>exo-dig</i> cyclization of
 3-sulfur-substituted 1,3-dien-5-ynes for synthesizing fulvenes and the
 <i>in situ</i> reaction with indoles.
;
_journal_issue                   7
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              2287
_journal_page_last               2291
_journal_paper_doi               10.1039/d5cc06478c
_journal_volume                  62
_journal_year                    2026
_chemical_formula_moiety         'C31 H31 N O'
_chemical_formula_sum            'C31 H31 N O'
_chemical_formula_weight         433.57
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2025-11-03
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-11-03 deposited with the CCDC.	2025-12-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.439(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.8475(10)
_cell_length_b                   18.7319(17)
_cell_length_c                   13.0573(13)
_cell_measurement_reflns_used    9514
_cell_measurement_temperature    230(2)
_cell_measurement_theta_max      68.40
_cell_measurement_theta_min      4.58
_cell_volume                     2486.1(4)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 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 2025/1 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      230.00
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0537
_diffrn_reflns_av_unetI/netI     0.0260
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            46875
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.510
_diffrn_reflns_theta_min         4.721
_diffrn_source_current           1.1
_diffrn_source_power             0.05500000000000001
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.528
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.5345
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1153 before and 0.0755 after correction.
The Ratio of minimum to maximum transmission is 0.7097.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.158
_exptl_crystal_description       prism
_exptl_crystal_F_000             928
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.503
_refine_diff_density_min         -0.471
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     334
_refine_ls_number_reflns         4537
_refine_ls_number_restraints     33
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0855
_refine_ls_R_factor_gt           0.0722
_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^)+(0.0850P)^2^+1.6110P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1818
_refine_ls_wR_factor_ref         0.1971
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3724
_reflns_number_total             4537
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc06478c2.cif
_cod_data_source_block           1_a
_cod_database_code               7135536
_shelx_shelxl_version_number     2025/1
_shelx_estimated_absorpt_t_max   0.979
_shelx_estimated_absorpt_t_min   0.902
_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
 C30-C29A
 1.54 with sigma of 0.003
 C31A-C29A
 1.54 with sigma of 0.003
 C31A-C30A
 1.54 with sigma of 0.003
 C30-C29 \\sim C30A-C29
 with sigma of 0.02
 C30-C31 \\sim C30A-C31A
 with sigma of 0.02
 C30-C29A \\sim C30A-C29A
 with sigma of 0.02
 C29-C31 \\sim C29-C31A
 with sigma of 0.04
 C31-C29A \\sim C31A-C29A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C31) = Uanis(C31A) = Uanis(C30) = Uanis(C30A)
4. Rigid body (RIGU) restrains
 C26, C25, C22, C23, C24
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C28)=Sof(H28A)=Sof(H28B)=1-FVAR(1)
 Sof(C28A)=Sof(H28C)=Sof(H28D)=FVAR(1)
 Sof(C29)=Sof(H29A)=Sof(H29B)=1-FVAR(2)
 Sof(C29A)=Sof(H29C)=Sof(H29D)=FVAR(2)
 Sof(C31A)=Sof(H31D)=Sof(H31E)=Sof(C30A)=Sof(H30C)=Sof(H30D)=Sof(H30E)=1-FVAR(3)
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C15(H15), C24(H24)
6.b Secondary CH2 refined with riding coordinates:
 C28(H28A,H28B), C30(H30A,H30B), C29(H29A,H29B), C28A(H28C,H28D), C29A(H29C,
 H29D), C31A(H31D,H31E)
6.c Aromatic/amide H refined with riding coordinates:
 C17(H17), C3(H3), C6(H6), C18(H18), C21(H21), C5(H5), C19(H19), C4(H4),
 C14(H14), C20(H20), C10(H10), C13(H13), C12(H12), C11(H11)
6.d Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C31(H31A,H31B,H31C), C30A(H30C,H30D,H30E)
;
_shelx_res_checksum              69140
_olex2_submission_special_instructions 'No special instructions were received'