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_7135535
_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         'C31.99 H31.973 Br N S'
_chemical_formula_sum            'C31.99 H32.06 Br N S'
_chemical_formula_weight         542.44
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2025-11-03
_audit_creation_method
;FinalCif V144 by Daniel Kratzert, Freiburg 2025, 
https://dkratzert.de/finalcif.html
;
_audit_update_record
;
2025-11-03 deposited with the CCDC.	2025-12-17 downloaded from the CCDC.
;
_cell_angle_alpha                80.973(15)
_cell_angle_beta                 83.02(2)
_cell_angle_gamma                87.953(16)
_cell_formula_units_Z            2
_cell_length_a                   8.016(3)
_cell_length_b                   12.509(3)
_cell_length_c                   14.522(4)
_cell_measurement_reflns_used    9835
_cell_measurement_temperature    239(2)
_cell_measurement_theta_max      72.25
_cell_measurement_theta_min      3.12
_cell_volume                     1427.3(8)
_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      239.00
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.970
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0633
_diffrn_reflns_av_unetI/netI     0.0355
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            42153
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.356
_diffrn_reflns_theta_min         3.103
_diffrn_source_current           1.1
_diffrn_source_power             0.05500000000000001
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    2.780
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.4758
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1378 before and 0.0864 after correction.
The Ratio of minimum to maximum transmission is 0.6314.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.262
_exptl_crystal_description       prism
_exptl_crystal_F_000             564
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.356
_refine_diff_density_min         -0.510
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     346
_refine_ls_number_reflns         5560
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0584
_refine_ls_R_factor_gt           0.0469
_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^)+(0.0551P)^2^+0.9520P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1153
_refine_ls_wR_factor_ref         0.1300
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4602
_reflns_number_total             5560
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc06478c2.cif
_cod_data_source_block           cm742f2e_0m_a
_cod_original_cell_volume        1427.2(7)
_cod_database_code               7135535
_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 C(H,H,H,H,H,H) groups
2. Others
 Sof(C31A)=Sof(H31C)=Sof(H31D)=Sof(H32D)=Sof(H32E)=Sof(H32F)=1-FVAR(1)
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(1)
 Fixed Sof: H30(0.8)
3.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C31(H31A,H31B), C31A(H31C,H31D), C30A(H30A,H30B), C29(H29A,
 H29B)
3.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C27(H27), C1(H1A), C23(H23), C4(H4), C3(H3), C15(H15), C26(H26),
 C24(H24), C21(H21), C17(H17), C20(H20), C19(H19), C30(H30), C18(H18)
3.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C28(H28A,H28B,H28C), C32(H32A,H32B,H32C), C32(H32D,H32E,
 H32F)
;
_olex2_submission_special_instructions 'No special instructions were received'
_shelx_shelxl_version_number     2025/1
_shelx_estimated_absorpt_t_min   0.606
_shelx_estimated_absorpt_t_max   0.973
_shelx_res_checksum              31209