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_7251651
_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 H21 Br F2 O6'
_chemical_formula_sum            'C16 H21 Br F2 O6'
_chemical_formula_weight         427.24
_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             2025-11-22
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-11-22 deposited with the CCDC.	2026-02-16 downloaded from the CCDC.
;
_cell_angle_alpha                108.466(4)
_cell_angle_beta                 106.202(4)
_cell_angle_gamma                93.974(4)
_cell_formula_units_Z            2
_cell_length_a                   7.2575(3)
_cell_length_b                   10.6800(5)
_cell_length_c                   12.7493(4)
_cell_measurement_reflns_used    4590
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.7750
_cell_measurement_theta_min      3.8470
_cell_volume                     886.50(7)
_computing_cell_refinement       'CrysAlisPro 1.171.44.128a (Rigaku OD, 2025)'
_computing_data_collection       'CrysAlisPro 1.171.44.128a (Rigaku OD, 2025)'
_computing_data_reduction        'CrysAlisPro 1.171.44.128a (Rigaku OD, 2025)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.955
_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     34.00  59.00   0.50    0.50    --  108.17 -61.00 -90.00   50
  2  \w     34.00  59.00   0.50    0.50    --  108.17 -55.00 -79.00   50
  3  \w     35.00  60.00   0.50    0.50    --  108.17 -61.00 -60.00   50
  4  \w     35.00  66.00   0.50    0.50    --  108.17 -61.00  60.00   62
  5  \w    -21.00   5.00   0.50    0.10    --   41.76 -19.00 120.00   52
  6  \w    100.00 148.00   0.50    0.50    --  108.17  55.00  63.00   96
  7  \w     87.00 157.00   0.50    0.50    --  108.17  45.00 150.00  140
  8  \w      0.00  26.00   0.50    0.10    --   41.76 -55.00 -79.00   52
  9  \w   -112.00 -23.00   0.50    0.10    --  -42.39 -55.00 -79.00  178
 10  \w   -112.00 -48.00   0.50    0.10    --  -42.39-179.00  90.00  128
 11  \w   -155.00-130.00   0.50    0.50    -- -108.80 -55.00 -79.00   50
 12  \w    -74.00 -49.00   0.50    0.50    -- -108.80  61.00 -90.00   50
 13  \w    -68.00 -38.00   0.50    0.50    -- -108.80  61.00-150.00   60
 14  \w    -66.00 -35.00   0.50    0.50    -- -108.80  55.00  63.00   62
 15  \w      4.00  31.00   0.50    0.10    --  -42.39  55.00  63.00   54
 16  \w     34.00  91.00   0.50    0.50    --  108.17 -95.00 -90.00  114
 17  \w     35.00  60.00   0.50    0.50    --  108.17 -95.00-150.00   50
 18  \w    106.00 161.00   0.50    0.50    --  108.17  28.00  38.00  110
 19  \w    -34.00  -8.00   0.50    0.10    --   42.14 -19.00 -60.00   52
 20  \w    -11.00  16.00   0.50    0.10    --   42.14 -99.00  90.00   54
 21  \w     -7.00  22.00   0.50    0.10    --   42.14 -19.00 -60.00   58
 22  \w     25.00  58.00   0.50    0.10    --   42.14 -99.00  90.00   66
 23  \w     15.00  41.00   0.50    0.10    --   42.14  77.00-120.00   52
 24  \w     68.00 100.00   0.50    0.10    --   42.14  77.00-120.00   64
 25  \w    -35.00  -4.00   0.50    0.10    --  -42.76  38.00  60.00   62
 26  \w    -45.00 -19.00   0.50    0.10    --  -42.76  38.00-180.00   52
 27  \w      9.00  34.00   0.50    0.10    --  -42.76  38.00-180.00   50
 28  \w      0.00  32.00   0.50    0.10    --  -42.76  38.00  60.00   64
 29  \w    -93.00 -42.00   0.50    0.10    --  -42.76 125.00  30.00  102
 30  \w     68.00  94.00   0.50    0.50    --  108.17 -77.00 -90.00   52
 31  \w     35.00  61.00   0.50    0.50    --  108.17 -77.00 -90.00   52
 32  \w     39.00 107.00   0.50    0.50    --  108.17-125.00  90.00  136
 33  \w     90.00 172.00   0.50    0.50    --  108.17  45.00   0.00  164
 34  \w     78.00 112.00   0.50    0.50    --  108.17-125.00-150.00   68
 35  \w     83.00 108.00   0.50    0.50    --  108.17-111.00 -11.27   50
 36  \w     69.00 105.00   0.50    0.50    --  108.17 -95.00  90.00   72
 37  \w     34.00  59.00   0.50    0.50    --  108.17 -61.00  90.00   50
 38  \w     39.00  65.00   0.50    0.50    --  108.17 -95.00  90.00   52
 39  \w   -107.00 -72.00   0.50    0.50    -- -108.80  77.00-150.00   70
 40  \w    -83.00 -38.00   0.50    0.50    -- -108.80 125.00-180.00   90
 41  \w   -125.00 -94.00   0.50    0.50    -- -108.80 -45.00-180.00   62
 42  \w   -172.00-135.00   0.50    0.50    -- -108.80 -45.00-180.00   74
 43  \w   -108.00 -45.00   0.50    0.50    -- -108.80 125.00 -30.00  126
 44  \w    -64.00 -39.00   0.50    0.50    -- -108.80 125.00-150.00   50
 45  \w   -110.00 -71.00   0.50    0.50    -- -108.80 125.00-150.00   78
 46  \w   -156.00 -89.00   0.50    0.50    -- -108.80 -61.00 150.00  134
 47  \w   -171.00-119.00   0.50    0.50    -- -108.80 -30.00 -60.00  104
 48  \w    -74.00 -49.00   0.50    0.50    -- -108.80  61.00  60.00   50
 49  \w    -66.00 -35.00   0.50    0.50    -- -108.80  77.00-150.00   62
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, SynergyCustom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1521333000
_diffrn_orient_matrix_UB_12      0.0696163000
_diffrn_orient_matrix_UB_13      -0.0362210000
_diffrn_orient_matrix_UB_21      -0.0826870000
_diffrn_orient_matrix_UB_22      0.1307596000
_diffrn_orient_matrix_UB_23      0.0332915000
_diffrn_orient_matrix_UB_31      0.1428006000
_diffrn_orient_matrix_UB_32      0.0435638000
_diffrn_orient_matrix_UB_33      0.1250439000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0471
_diffrn_reflns_av_unetI/netI     0.0459
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            8636
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.484
_diffrn_reflns_theta_min         3.856
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.626
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65319
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.128a (Rigaku Oxford Diffraction, 2025)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_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    1.601
_exptl_crystal_description       block
_exptl_crystal_F_000             436
_exptl_crystal_size_max          0.02
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.437
_refine_diff_density_min         -1.075
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     229
_refine_ls_number_reflns         3504
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0701
_refine_ls_R_factor_gt           0.0611
_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^)+(0.0789P)^2^+2.7294P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1567
_refine_ls_wR_factor_ref         0.1610
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3117
_reflns_number_total             3504
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5gc06365e2.cif
_cod_data_source_block           hjg2_auto
_cod_depositor_comments
'Adding full bibliography for 7251650--7251651.cif.'
_cod_database_code               7251651
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O F Br'
_cell_oxdiff_angle_alpha         108.466(4)
_cell_oxdiff_angle_beta          106.202(4)
_cell_oxdiff_angle_gamma         93.974(4)
_cell_oxdiff_length_a            7.2575(3)
_cell_oxdiff_length_b            10.6800(5)
_cell_oxdiff_length_c            12.7493(4)
_cell_oxdiff_measurement_reflns_used 4590
_cell_oxdiff_volume              886.49(6)
_shelx_estimated_absorpt_t_max   0.931
_shelx_estimated_absorpt_t_min   0.931
_diffrn_oxdiff_digest_hkl
;
437f6d5c5400359308e67673577e65b93260e2
;
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name hjg2.par
_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:
 C7(H7), C3(H3), C12(H12), C4(H4)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C2(H2A,H2B), C15(H15A,H15B), C5(H5A,H5B)
2.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C)
;
_shelx_res_checksum              78972
_shelx_hkl_checksum              12963
_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 2.484
_oxdiff_exptl_absorpt_empirical_full_min 0.375