Ni-catalyzed highly regioselective carboborylation bifunctionalization of allenes: access to α-substituted-γ-boro-δ-enoates.
Wu, Jing; Guo, Xinman; Zou, Jinghan; Wang, Ziyu; Chang, Weixing; Liu, Lingyan; Li, Jing; Organic & biomolecular chemistry 23 (2025) 3894–3898; doi:10.1039/d5ob00364d

data_7160434
_publ_section_title
;
 Ni-catalyzed highly regioselective carboborylation bifunctionalization of
 allenes: access to &#x3b1;-substituted-&#x3b3;-boro-&#x3b4;-enoates.
;
_journal_issue                   16
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3894
_journal_page_last               3898
_journal_paper_doi               10.1039/d5ob00364d
_journal_volume                  23
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         '0.5(C29 H38 N O3), 0.5(C29 H36 N O3)'
_chemical_formula_sum            'C29 H37 N O3'
_chemical_formula_weight         447.59
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-11-07
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-24 deposited with the CCDC.	2025-03-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.508(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.7654(4)
_cell_length_b                   10.6359(5)
_cell_length_c                   24.7507(9)
_cell_measurement_reflns_used    16487
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.2920
_cell_measurement_theta_min      3.5360
_cell_volume                     2565.89(19)
_computing_cell_refinement       'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.136a 64-bit (release 23-08-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_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 2018/2 (Sheldrick, 2018)'
_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-Arc 150'
_diffrn_measured_fraction_theta_full 0.942
_diffrn_measured_fraction_theta_max 0.935
_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     60.00  85.00   0.50    0.65    --   53.75  47.00 -76.00   50
  2  \w     -1.00  24.00   0.50    0.65    --   53.75 -47.00 134.00   50
  3  \w    -87.00 -61.00   0.50    0.65    --  -54.47 -47.00 134.00   52
  4  \w    -34.00  -9.00   0.50    0.65    --  -54.47  47.00 -76.00   50
  5  \w     92.00 119.00   0.50    0.65    --   61.90  47.00 -76.00   54
  6  \w    -34.00  -8.00   0.50    0.65    --  -63.44  47.00 -76.00   52
  7  \w   -117.00 -92.00   0.50    0.65    --  -63.44 -47.00 134.00   50
  8  \w   -128.00 -93.00   0.50    0.65    --  -77.78 -47.00 134.00   70
  9  \w    106.00 146.00   0.50    3.00    --   93.51  47.00 -76.00   80
 10  \w    -59.00 -34.00   0.50    0.65    --  -54.47  77.00 -90.00   50
 11  \w   -122.00 -39.00   0.50    0.65    --  -63.44 -15.00 -30.00  166
 12  \w    -68.00 -21.00   0.50    0.65    --  -63.44  77.00  30.00   94
 13  \w    -66.00 -20.00   0.50    0.65    --  -63.44  77.00 -30.00   92
 14  \w   -123.00 -97.00   0.50    0.65    --  -77.78 -61.00-180.00   52
 15  \w    -52.00 -26.00   0.50    0.65    --  -77.78  61.00-150.00   52
 16  \w    -54.00 -27.00   0.50    0.65    --  -77.78  61.00 -90.00   54
 17  \w    -53.00 -27.00   0.50    0.65    --  -77.78  61.00 150.00   52
 18  \w    -67.00 -41.00   0.50    0.65    --  -77.78  77.00-120.00   52
 19  \w   -118.00 -88.00   0.50    0.65    --  -77.78 -61.00 -60.00   60
 20  \w    -51.00 -25.00   0.50    0.65    --  -77.78  61.00 120.00   52
 21  \w    100.00 145.00   0.50    3.00    --   93.51  61.00-180.00   90
 22  \w     44.00  88.00   0.50    3.00    --   93.51 -94.00-120.00   88
 23  \w     44.00  92.00   0.50    3.00    --   93.51 -94.00  30.00   96
 24  \w    109.00 134.00   0.50    3.00    --   93.51  61.00 120.00   50
 25  \w     44.00  83.00   0.50    3.00    --   93.51 -94.00  90.00   78
 26  \w    122.00 148.00   0.50    3.00    --   93.51 111.00-150.00   52
 27  \w    110.00 135.00   0.50    3.00    --   93.51 111.00-180.00   50
 28  \w     98.00 123.00   0.50    3.00    --   93.51 111.00 150.00   50
 29  \w     97.00 144.00   0.50    3.00    --   93.51  61.00  30.00   94
 30  \w     41.00  88.00   0.50    3.00    --   93.51-111.00 -30.00   94
 31  \w     98.00 130.00   0.50    3.00    --   93.51  45.00 -30.00   64
 32  \w     98.00 126.00   0.50    3.00    --   93.51  61.00 -30.00   56
 33  \w     47.00  84.00   0.50    3.00    --   93.51 -94.00 -90.00   74
 34  \w    102.00 127.00   0.50    3.00    --   93.51  15.00 150.00   50
 35  \w     43.00  68.00   0.50    3.00    --   93.51 -94.00 -60.00   50
 36  \w    103.00 130.00   0.50    3.00    --   93.51  61.00 150.00   54
 37  \w     59.00  90.00   0.50    3.00    --   93.51 -94.00-150.00   62
 38  \w     49.00  87.00   0.50    3.00    --   93.51-111.00  90.00   76
 39  \w     45.00  87.00   0.50    3.00    --   93.51 -94.00 150.00   84
 40  \w     52.00  77.00   0.50    3.00    --   93.51-111.00  60.00   50
 41  \w    101.00 144.00   0.50    3.00    --   93.51  61.00   0.00   86
 42  \w     44.00  70.00   0.50    3.00    --   93.51 -94.00-180.00   52
 43  \w     51.00  85.00   0.50    3.00    --   93.51  15.00 150.00   68
 44  \w     45.00  72.00   0.50    3.00    --   93.51 -94.00  60.00   54
 45  \w    120.00 147.00   0.50    3.00    --   93.51 111.00  30.00   54
 46  \w    106.00 131.00   0.50    3.00    --   93.51  45.00   0.00   50
 47  \w     55.00  81.00   0.50    0.65    --   62.22  15.00-150.00   52
 48  \w     15.00  40.00   0.50    0.65    --   14.00  64.00  76.57   50
 49  \w     30.00  56.00   0.50    0.65    --   26.00  55.00  90.59   52
 50  \w     28.00  53.00   0.50    0.65    --   26.00  61.00  57.73   50
 51  \w    -83.00 -57.00   0.50    0.65    --  -50.00 -50.00  -5.15   52
 52  \w    -80.00 -54.00   0.50    0.65    --  -50.00 -50.00 -13.74   52
 53  \w     57.00  82.00   0.50    0.65    --   53.96  45.00  30.00   50
 54  \w     65.00  92.00   0.50    0.65    --   53.96  45.00 -30.00   54
 55  \w     -3.00  22.00   0.50    0.65    --   53.96 -45.00 -60.00   50
 56  \w     63.00  91.00   0.50    0.65    --   53.96  45.00  90.00   56
 57  \w    -86.00 -60.00   0.50    0.65    --  -54.00 -49.00 -20.29   52
 58  \w    -90.00 -64.00   0.50    0.65    --  -58.00 -50.00   8.34   52
 59  \w    -88.00 -61.00   0.50    0.65    --  -58.00 -48.00 -29.44   54
 60  \w     60.00  85.00   0.50    0.65    --   58.09  44.00  84.27   50
 61  \w     61.00  86.00   0.50    0.65    --   58.09  54.00  52.12   50
 62  \w     65.00 115.00   0.50    0.65    --   62.22  45.00  90.00  100
 63  \w   -100.00 -74.00   0.50    0.65    --  -63.67 -45.00 -30.00   52
 64  \w    -32.00  -7.00   0.50    0.65    --  -63.67  45.00-150.00   50
 65  \w    -32.00  -7.00   0.50    0.65    --  -63.67  45.00  30.00   50
 66  \w    -97.00 -71.00   0.50    0.65    --  -66.00 -49.00  42.37   52
 67  \w   -104.00 -78.00   0.50    0.65    --  -74.00 -49.00 -40.26   52
 68  \w   -113.00 -87.00   0.50    0.65    --  -77.77 -61.00  60.00   52
 69  \w    -49.00 -24.00   0.50    0.65    --  -77.77 111.00-180.00   50
 70  \w   -110.00 -84.00   0.50    0.65    --  -77.77 -45.00   0.00   52
 71  \w   -114.00 -88.00   0.50    0.65    --  -77.77 -61.00   0.00   52
 72  \w    -82.00 -56.00   0.50    0.65    --  -77.77 111.00-180.00   52
 73  \w    -55.00 -29.00   0.50    0.65    --  -77.77 111.00 -90.00   52
 74  \w    -59.00 -24.00   0.50    0.65    --  -77.77 111.00 120.00   70
 75  \w    -90.00 -64.00   0.50    0.65    --  -77.77 111.00 120.00   52
 76  \w    -92.00 -62.00   0.50    0.65    --  -77.77 111.00 -90.00   60
 77  \w   -111.00 -86.00   0.50    3.00    --  -82.00 -61.00  -3.85   50
 78  \w   -117.00 -91.00   0.50    3.00    --  -82.00 -53.00 -24.20   52
 79  \w   -110.00 -85.00   0.50    3.00    --  -82.00 -54.00   5.47   50
 80  \w   -120.00 -87.00   0.50    3.00    --  -82.00 -61.00 -22.80   66
 81  \w   -112.00 -86.00   0.50    3.00    --  -82.00 -61.00  57.12   52
 82  \w   -111.00 -85.00   0.50    3.00    --  -82.00 -55.00  23.78   52
 83  \w   -136.00 -89.00   0.50    3.00    --  -82.00 -54.00  -1.62   94
 84  \w   -135.00 -86.00   0.50    3.00    --  -82.00 -61.00  70.78   98
 85  \w     40.00  65.00   0.50    3.00    --   93.50-111.00-150.00   50
 86  \w     43.00  68.00   0.50    3.00    --   93.50 -94.00-150.00   50
 87  \w     96.00 122.00   0.50    3.00    --   93.50  45.00 150.00   52
 88  \w     96.00 121.00   0.50    3.00    --   93.50  45.00   0.00   50
 89  \w    117.00 143.00   0.50    3.00    --   93.50 111.00-180.00   52
 90  \w    115.00 141.00   0.50    3.00    --   93.50 111.00 -30.00   52
 91  \w    110.00 136.00   0.50    3.00    --   93.50  61.00-120.00   52
 92  \w    110.00 138.00   0.50    3.00    --   93.50 111.00 -60.00   56
 93  \w    108.00 133.00   0.50    3.00    --   93.50  15.00  60.00   50
 94  \w     95.00 120.00   0.50    3.00    --   93.50  61.00  90.00   50
 95  \w     95.00 120.00   0.50    3.00    --   93.50  61.00   0.00   50
 96  \w     96.00 130.00   0.50    3.00    --   93.50  45.00  90.00   68
 97  \w    101.00 140.00   0.50    3.00    --   93.50 111.00-120.00   78
 98  \w     46.00  92.00   0.50    3.00    --   93.50 -94.00 120.00   92
 99  \w     63.00  89.00   0.50    3.00    --   93.50 -94.00 -60.00   52
100  \w     96.00 145.00   0.50    3.00    --   93.50  45.00  60.00   98
101  \w     44.00  87.00   0.50    3.00    --   93.50 -94.00 -90.00   86
102  \w     67.00  93.00   0.50    3.00    --   93.50-111.00 120.00   52
103  \w     95.00 147.00   0.50    3.00    --   93.50  61.00  60.00  104
104  \w     40.00  66.00   0.50    3.00    --   93.50-111.00 150.00   52
105  \w    125.00 150.00   0.50    3.00    --   93.50  30.00   0.00   50
106  \w    123.00 151.00   0.50    3.00    --   93.50  30.00  60.00   56
107  \w    108.00 133.00   0.50    3.00    --   93.50 111.00  90.00   50
108  \w     43.00  68.00   0.50    3.00    --   93.50 -94.00 -30.00   50
109  \w     43.00  68.00   0.50    3.00    --   93.50 -94.00  30.00   50
110  \w     96.00 121.00   0.50    3.00    --   93.50  45.00  30.00   50
111  \w    103.00 131.00   0.50    3.00    --   93.50  45.00 -90.00   56
112  \w    117.00 142.00   0.50    3.00    --   93.50 111.00 150.00   50
113  \w     40.00  65.00   0.50    3.00    --   93.50-111.00  60.00   50
114  \w     40.00  65.00   0.50    3.00    --   93.50-111.00 -90.00   50
115  \w     41.00  75.00   0.50    3.00    --   93.50-111.00-120.00   68
116  \w     95.00 120.00   0.50    3.00    --   93.50  61.00  30.00   50
117  \w     95.00 120.00   0.50    3.00    --   93.50  61.00 -60.00   50
118  \w     62.00  87.00   0.50    3.00    --   93.50 -94.00  60.00   50
119  \w    117.00 143.00   0.50    3.00    --   93.50  30.00-150.00   52
120  \w    114.00 139.00   0.50    3.00    --   93.50 111.00   0.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1039685000
_diffrn_orient_matrix_UB_12      -0.0735692000
_diffrn_orient_matrix_UB_13      0.0319146000
_diffrn_orient_matrix_UB_21      -0.0766552000
_diffrn_orient_matrix_UB_22      -0.0399601000
_diffrn_orient_matrix_UB_23      -0.0535213000
_diffrn_orient_matrix_UB_31      0.0912508000
_diffrn_orient_matrix_UB_32      -0.1182918000
_diffrn_orient_matrix_UB_33      -0.0019624000
_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  0.0782
_diffrn_reflns_av_unetI/netI     0.0467
_diffrn_reflns_Laue_measured_fraction_full 0.942
_diffrn_reflns_Laue_measured_fraction_max 0.935
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            43247
_diffrn_reflns_point_group_measured_fraction_full 0.858
_diffrn_reflns_point_group_measured_fraction_max 0.844
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.420
_diffrn_reflns_theta_min         4.536
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.579
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92053
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.136a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.159
_exptl_crystal_description       needle
_exptl_crystal_F_000             968
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.604
_refine_diff_density_min         -0.329
_refine_diff_density_rms         0.068
_refine_ls_abs_structure_details
;
 Flack x determined using 2392 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.1(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     632
_refine_ls_number_reflns         9096
_refine_ls_number_restraints     66
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.1191
_refine_ls_R_factor_gt           0.1073
_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^)+(0.1034P)^2^+5.0703P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2661
_refine_ls_wR_factor_ref         0.2757
_reflns_Friedel_coverage         0.710
_reflns_Friedel_fraction_full    0.764
_reflns_Friedel_fraction_max     0.743
_reflns_number_gt                7900
_reflns_number_total             9096
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.9739\% 
around [-0.00 0.00 1.00] (reciprocal) or [0.15 0.01 0.99] (direct)
;
_cod_data_source_file            d5ob00364d2.cif
_cod_data_source_block           37-cr-20241105d_twin1_hklf4
_cod_depositor_comments          'Adding full bibliography for 7160434.cif.'
_cod_database_code               7160434
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C28H38BNO3
_shelx_estimated_absorpt_t_max   0.977
_shelx_estimated_absorpt_t_min   0.939
_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
 N007-H007 = N006-H006
 0.9 with sigma of 0.01
 C01S-C01R \\sim C3-C01R
 with sigma of 0.01
 C01U-C01S \\sim C3-C10
 with sigma of 0.01
 C10-C01L \\sim C01U-C01L
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C01S \\sim C01U \\sim C3 \\sim C10: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(C01S) \\sim Ueq, Uanis(C01U) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C10)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(C10)=Sof(H10A)=Sof(H10B)=1-FVAR(1)
 Sof(C01S)=Sof(H01O)=Sof(H01P)=Sof(C01U)=Sof(H01Q)=Sof(H01R)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C00G(H00M), C00K(H00K)
5.b Secondary CH2 refined with riding coordinates:
 C00F(H00J,H00L), C00Q(H00U,H00W), C00T(H00Y,H), C00U(H00Z,HA), C00W(H00H,
 H00I), C013(H01A,H01B), C015(H01S,H01U), C01S(H01O,H01P), C01U(H01Q,H01R),
 C3(H3A,H3B), C10(H10A,H10B)
5.c Aromatic/amide H refined with riding coordinates:
 C00B(H00B), C00H(H00O), C00L(H00P), C00N(H00N), C00P(H00T), C00S(H00X),
 C00V(H00V), C00X(H00), C011(H011), C012(H012), C014(H014), C016(H016),
 C019(H019), C01F(H1), C01G(H01G), C01I(H2), C01J(H3), C01M(H01M), C01N(H01N),
 C01O(H4), C01Q(H5), C01T(H01T)
5.d Idealised Me refined as rotating group:
 C00E(H00A,H00C,H00D), C00O(H00Q,H00R,H00S), C00R(H00E,H00F,H00G), C017(H01V,
 H01W,H01X), C018(H01Y,HB,HC), C01A(H01C,H01D,H01E), C01C(H01Z,HD,HE), C01E(H01,
 HF,HG), C01H(H01F,H01H,H01I), C01K(H01J,H01K,H01L)
;
_shelx_res_checksum              59415
_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 1.841
_oxdiff_exptl_absorpt_empirical_full_min 0.611
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2