Enantioselective cyclization of bromoenynes: mechanistic understanding of gold(i)-catalyzed alkoxycyclizations.
Cataffo, Andrea; García-Padilla, Eduardo; Escofet, Imma; Fincias, Nicolás; Arnanz, Anna; Zuccarello, Giuseppe; Tian, Guilong; Cai, Luyu; Khorasanidarehdor, Fereshteh; Maseras, Feliu; Echavarren, Antonio M.; Chemical science 17 (2026) 5005–5015; doi:10.1039/d5sc09023g

data_1576853
_publ_section_title
;
 Enantioselective cyclization of bromoenynes: mechanistic understanding of
 gold(i)-catalyzed alkoxycyclizations.
;
_journal_issue                   10
_journal_name_full               'Chemical science'
_journal_page_first              5005
_journal_page_last               5015
_journal_paper_doi               10.1039/d5sc09023g
_journal_volume                  17
_journal_year                    2026
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C14 H17 Br O'
_chemical_formula_sum            'C14 H17 Br O'
_chemical_formula_weight         281.18
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-01
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2024-03-05 deposited with the CCDC.	2026-01-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.2267(12)
_cell_length_b                   11.976(2)
_cell_length_c                   14.973(3)
_cell_measurement_reflns_used    6559
_cell_measurement_temperature    100.40
_cell_measurement_theta_max      30.46
_cell_measurement_theta_min      2.72
_cell_volume                     1295.9(4)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'XT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.40
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0303
_diffrn_reflns_av_unetI/netI     0.0283
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            14021
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.612
_diffrn_reflns_theta_min         2.178
_diffrn_source_current           0.61
_diffrn_source_power             0.0305
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.150
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.5945
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0963 before and 0.0397 after correction.
The Ratio of minimum to maximum transmission is 0.7968.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.441
_exptl_crystal_description       block
_exptl_crystal_F_000             576
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.441
_refine_diff_density_min         -0.401
_refine_diff_density_rms         0.057
_refine_ls_abs_structure_details
;
 Flack x determined using 1387 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.007(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     148
_refine_ls_number_reflns         3880
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0298
_refine_ls_R_factor_gt           0.0249
_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^)+(0.0324P)^2^+0.2898P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0634
_refine_ls_wR_factor_ref         0.0653
_reflns_Friedel_coverage         0.732
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.959
_reflns_number_gt                3516
_reflns_number_total             3880
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09023g2.cif
_cod_data_source_block           mo_ac013061b_0m
_cod_database_code               1576853
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.744
_shelx_estimated_absorpt_t_min   0.452
_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.a Ternary CH refined with riding coordinates:
 C3(H3)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C6(H6), C7(H7), C8(H8), C9(H9)
2.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              32766
_olex2_submission_special_instructions 'No special instructions were received'