Solvent-controlled divergent 1,2-dialkylation and 1,1,2-bromodialkylation of terminal alkynes to access difluoroalkylated cyclopentanes
Han, Jianguo; Lang, Yatao; Zhu, Chen; Yue, Huifeng; Green Chemistry 28 (2026) 4842–4849; doi:10.1039/D5GC06365E

data_7251650
_publ_section_title
;
 Solvent-controlled divergent 1,2-dialkylation and 1,1,2-bromodialkylation
 of terminal alkynes to access difluoroalkylated cyclopentanes
;
_journal_issue                   11
_journal_name_full               'Green Chemistry'
_journal_page_first              4842
_journal_page_last               4849
_journal_paper_doi               10.1039/D5GC06365E
_journal_volume                  28
_journal_year                    2026
_chemical_formula_moiety         'C16 H24 F2 O4'
_chemical_formula_sum            'C16 H24 F2 O4'
_chemical_formula_weight         318.35
_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
_audit_creation_date             2025-11-19
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-11-19 deposited with the CCDC.	2026-02-16 downloaded from the CCDC.
;
_cell_angle_alpha                69.361(14)
_cell_angle_beta                 75.835(10)
_cell_angle_gamma                88.474(12)
_cell_formula_units_Z            2
_cell_length_a                   7.0533(8)
_cell_length_b                   10.1731(16)
_cell_length_c                   13.3163(16)
_cell_measurement_reflns_used    3105
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      23.1280
_cell_measurement_theta_min      3.1210
_cell_volume                     865.1(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.827
_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     53.00  79.00   0.50   18.00    --    5.00  55.00 -30.00   52
  2  \w    -81.00 -56.00   0.50   18.00    --   -9.80  55.00-150.00   50
  3  \w    -18.00  79.00   0.50   18.00    --   -9.80  55.00  60.00  194
  4  \w    -72.00 -46.00   0.50   18.00    --   -9.80  55.00 -30.00   52
  5  \w    -18.00  65.00   0.50   18.00    --   -9.80  55.00 -30.00  166
  6  \w    -60.00 -35.00   0.50   18.00    --   -9.80  55.00  60.00   50
  7  \w    -26.00  79.00   0.50   18.00    --   -9.80  55.00-150.00  210
  8  \w    -23.00  77.00   0.50   18.00    --   -9.80  43.00  90.00  200
  9  \w    -70.00 -44.00   0.50   18.00    --   -9.80  43.00  90.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0450702000
_diffrn_orient_matrix_UB_12      -0.0095367000
_diffrn_orient_matrix_UB_13      -0.0392944000
_diffrn_orient_matrix_UB_21      -0.0544005000
_diffrn_orient_matrix_UB_22      -0.0607757000
_diffrn_orient_matrix_UB_23      0.0415351000
_diffrn_orient_matrix_UB_31      -0.0762430000
_diffrn_orient_matrix_UB_32      0.0423138000
_diffrn_orient_matrix_UB_33      0.0137602000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0468
_diffrn_reflns_av_unetI/netI     0.0557
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.827
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            11064
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.827
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.561
_diffrn_reflns_theta_min         2.985
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.100
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69975
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear whiteish white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.222
_exptl_crystal_description       block
_exptl_crystal_F_000             340
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.575
_refine_diff_density_min         -0.300
_refine_diff_density_rms         0.100
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.207
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     204
_refine_ls_number_reflns         4002
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.207
_refine_ls_R_factor_all          0.1599
_refine_ls_R_factor_gt           0.1171
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3274
_refine_ls_wR_factor_ref         0.3547
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2327
_reflns_number_total             4002
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5gc06365e2.cif
_cod_data_source_block           hjg
_cod_depositor_comments
'Adding full bibliography for 7251650--7251651.cif.'
_cod_database_code               7251650
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_shelx_estimated_absorpt_t_max   0.990
_shelx_estimated_absorpt_t_min   0.990
_diffrn_oxdiff_ac3_digest_hkl    41ad7080764430c8659189187ca88727f911b1
_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:
 C4(H4)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2a,H2b), C5(H5a,H5b), C12(H12a,H12b), C15(H15a,H15b)
2.c Idealised Me refined as rotating group:
 C6(H6a,H6b,H6c), C9(H9a,H9b,H9c), C7(H7a,H7b,H7c), C11(H11a,H11b,H11c),
 C16(H16a,H16b,H16c)
;
_shelx_res_checksum              28262
_shelx_hkl_checksum              74597
_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 1.275
_oxdiff_exptl_absorpt_empirical_full_min 0.826