Regio- and stereoselective copper-catalyzed α,β-protoboration of allenoates: access to <i>Z</i>-β,γ-unsaturated β-boryl esters.
Szwetkowski, Connor; Slebodnick, Carla; Santos, Webster L.; Organic & biomolecular chemistry 20 (2022) 3287–3291; doi:10.1039/d2ob00423b

data_7158618
_publ_section_title
;
 Regio- and stereoselective copper-catalyzed \a,\b-protoboration of
 allenoates: access to <i>Z</i>-\b,\g-unsaturated \b-boryl esters.
;
_journal_issue                   16
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3287
_journal_page_last               3291
_journal_paper_doi               10.1039/d2ob00423b
_journal_volume                  20
_journal_year                    2022
_chemical_formula_moiety         'C16 H22 B N O3, C H Cl3'
_chemical_formula_sum            'C17 H23 B Cl3 N O3'
_chemical_formula_weight         406.52
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-01-18
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2021-10-08 deposited with the CCDC.	2022-03-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.856(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.8732(3)
_cell_length_b                   23.4482(5)
_cell_length_c                   10.7330(3)
_cell_measurement_reflns_used    12688
_cell_measurement_temperature    99.99(13)
_cell_measurement_theta_max      77.4010
_cell_measurement_theta_min      3.7460
_cell_volume                     2100.35(11)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (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      99.99(13)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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    -35.00   1.00   0.50    1.00    --  -46.87  76.00 128.00   72
  2  \w   -119.00 -29.00   0.50    1.00    --  -46.87 -76.00   2.00  180
  3  \w    -14.00  68.00   0.50    1.00    --   46.87 -76.00   2.00  164
  4  \w     25.00 113.00   0.50    1.00    --   46.87  76.00 128.00  176
  5  \w   -113.00 -67.00   0.50    5.00    --  -88.50 -76.00   2.00   92
  6  \w    -85.00 -59.00   0.50    5.00    --  -88.50  76.00 128.00   52
  7  \w     87.00 137.00   0.50    5.00    --  110.00  76.00 128.00  100
  8  \w     56.00  83.00   0.50    5.00    --  110.00 -76.00   2.00   54
  9  \w    -29.00   0.00   0.50    1.00    --  -46.87  19.00  90.00   58
 10  \w   -118.00 -87.00   0.50    1.00    --  -46.87-125.00 -60.00   62
 11  \w   -120.00 -93.00   0.50    1.00    --  -46.87-125.00  90.00   54
 12  \w     88.00 114.00   0.50    1.00    --   46.87  77.00-150.00   52
 13  \w     41.00  94.00   0.50    1.00    --   46.87-125.00-150.00  106
 14  \w   -159.00 -90.00   0.50    5.00    --  -88.50 -94.00 120.00  138
 15  \w     39.00  67.00   0.50    5.00    --  110.00 -94.00 120.00   56
 16  \w    133.00 159.00   0.50    5.00    --  110.00  77.00  30.00   52
 17  \w    108.00 140.00   0.50    5.00    --  110.00 125.00 -30.00   64
 18  \w     93.00 118.00   0.50    5.00    --  110.00  15.00-150.00   50
 19  \w    128.00 177.00   0.50    5.00    --  110.00  15.00-150.00   98
 20  \w     66.00  99.00   0.50    5.00    --  110.00 -94.00  60.00   66
 21  \w     42.00  80.00   0.50    5.00    --  110.00 -94.00  30.00   76
 22  \w     74.00 104.00   0.50    5.00    --  110.00 -94.00   0.00   60
 23  \w     38.00 102.00   0.50    5.00    --  110.00 -94.00-120.00  128
 24  \w     97.00 127.00   0.50    5.00    --  110.00  77.00  30.00   60
 25  \w     77.00 109.00   0.50    5.00    --  110.00-113.00 -30.62   64
 26  \w     70.00 112.00   0.50    5.00    --  110.00-125.00-120.00   84
 27  \w    115.00 175.00   0.50    5.00    --  110.00 125.00 -90.00  120
 28  \w     38.00  68.00   0.50    5.00    --  110.00 -61.00   0.00   60
 29  \w     45.00  90.00   0.50    5.00    --  110.00-144.00 147.06   90
 30  \w    138.00 168.00   0.50    5.00    --  110.00  45.00 -30.00   60
 31  \w     55.00 103.00   0.50    5.00    --  110.00 -94.00 -60.00   96
 32  \w     94.00 126.00   0.50    5.00    --  110.00  15.00  60.00   64
 33  \w    133.00 176.00   0.50    5.00    --  110.00  15.00  60.00   86
 34  \w     57.00 108.00   0.50    5.00    --  110.00-125.00-150.00  102
 35  \w    108.00 154.00   0.50    5.00    --  110.00  30.00  90.00   92
 36  \w    101.00 146.00   0.50    5.00    --  110.00  45.00 120.00   90
 37  \w     38.00  63.00   0.50    5.00    --  110.00 -61.00 120.00   50
 38  \w     58.00  97.00   0.50    5.00    --  110.00 -77.00  60.00   78
 39  \w     40.00 106.00   0.50    5.00    --  110.00 -94.00 -30.00  132
 40  \w     53.00  92.00   0.50    5.00    --  110.00 -94.00 -90.00   78
 41  \w     40.00  65.00   0.50    5.00    --  110.00-125.00-120.00   50
 42  \w     42.00  68.00   0.50    5.00    --  110.00 -61.00  30.00   52
 43  \w    122.00 173.00   0.50    5.00    --  110.00  45.00 -90.00  102
 44  \w     73.00 108.00   0.50    5.00    --  110.00-108.00  65.17   70
 45  \w     81.00 106.00   0.50    5.00    --  110.00 -94.00 120.00   50
 46  \w     56.00  85.00   0.50    5.00    --  110.00-125.00  30.00   58
 47  \w     97.00 176.00   0.50    5.00    --  110.00  30.00 -60.00  158
 48  \w     78.00 103.00   0.50    5.00    --  110.00 -77.00  90.00   50
 49  \w     66.00  99.00   0.50    5.00    --  110.00 -94.00  90.00   66
 50  \w     61.00  86.00   0.50    5.00    --  110.00-140.00 -53.78   50
 51  \w     90.00 122.00   0.50    5.00    --  110.00-140.00 -53.78   64
 52  \w     96.00 134.00   0.50    5.00    --  110.00  45.00 -30.00   76
 53  \w    145.00 171.00   0.50    5.00    --  110.00 125.00 -30.00   52
 54  \w     92.00 137.00   0.50    5.00    --  110.00  77.00 -30.00   90
 55  \w    145.00 177.00   0.50    5.00    --  110.00  77.00 -30.00   64
 56  \w     41.00  66.00   0.50    5.00    --  110.00 -61.00 -90.00   50
 57  \w     45.00 103.00   0.50    1.00    --   46.87  57.00-150.00  116
 58  \w   -116.00 -88.00   0.50    1.00    --  -46.87-125.00 -30.00   56
 59  \w     85.00 110.00   0.50    1.00    --   46.87  77.00 -60.00   50
 60  \w     38.00  74.00   0.50    5.00    --  110.00-125.00  90.00   72
 61  \w    148.00 174.00   0.50    5.00    --  110.00  77.00-120.00   52
 62  \w    148.00 175.00   0.50    5.00    --  110.00  45.00  90.00   54
 63  \w    102.00 133.00   0.50    5.00    --  110.00  30.00-150.00   62
 64  \w    152.00 177.00   0.50    5.00    --  110.00  30.00-150.00   50
 65  \w     88.00 130.00   0.50    5.00    --  110.00  77.00-120.00   84
 66  \w     38.00  64.00   0.50    5.00    --  110.00-125.00 120.00   52
 67  \w    100.00 126.00   0.50    5.00    --  110.00  45.00  90.00   52
 68  \w    131.00 160.00   0.50    5.00    --  110.00  30.00-120.00   58
 69  \w     95.00 133.00   0.50    5.00    --  110.00 125.00   0.00   76
 70  \w    116.00 160.00   0.50    5.00    --  110.00  77.00 -90.00   88
 71  \w     98.00 129.00   0.50    5.00    --  110.00  45.00-120.00   62
 72  \w     98.00 124.00   0.50    5.00    --  110.00  61.00-180.00   52
 73  \w    142.00 169.00   0.50    5.00    --  110.00  61.00-180.00   54
 74  \w     98.00 124.00   0.50    5.00    --  110.00  30.00-120.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1735985000
_diffrn_orient_matrix_UB_12      0.0222681000
_diffrn_orient_matrix_UB_13      -0.0537551000
_diffrn_orient_matrix_UB_21      0.0542158000
_diffrn_orient_matrix_UB_22      0.0496880000
_diffrn_orient_matrix_UB_23      -0.0686452000
_diffrn_orient_matrix_UB_31      -0.0319004000
_diffrn_orient_matrix_UB_32      -0.0367586000
_diffrn_orient_matrix_UB_33      -0.1253110000
_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  0.0834
_diffrn_reflns_av_unetI/netI     0.0587
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            16596
_diffrn_reflns_point_group_measured_fraction_full 0.898
_diffrn_reflns_point_group_measured_fraction_max 0.877
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.070
_diffrn_reflns_theta_min         3.770
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.074
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.341
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.286
_exptl_crystal_description       needle
_exptl_crystal_F_000             848
_exptl_crystal_recrystallization_method 'crystallized from CHCl3'
_exptl_crystal_size_max          0.41
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.523
_refine_diff_density_min         -0.333
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.05(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.148
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     237
_refine_ls_number_reflns         3935
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.148
_refine_ls_R_factor_all          0.0557
_refine_ls_R_factor_gt           0.0535
_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^)+(0.0882P)^2^+1.0521P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1462
_refine_ls_wR_factor_ref         0.1481
_reflns_Friedel_coverage         0.761
_reflns_Friedel_fraction_full    0.795
_reflns_Friedel_fraction_max     0.760
_reflns_number_gt                3706
_reflns_number_total             3935
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ob00423b2.cif
_cod_data_source_block           cs2641
_cod_depositor_comments          'Adding full bibliography for 7158618.cif.'
_cod_database_code               7158618
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C16 H22 B N O3 C H Cl3'
_chemical_oxdiff_usercomment     'Connor Szwetkowski/Santos (CDS-5-62)'
_shelx_estimated_absorpt_t_max   0.822
_shelx_estimated_absorpt_t_min   0.286
_reflns_odcompleteness_completeness 99.61
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     77.17
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.95(3)
 0.05(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3.a Ternary CH refined with riding coordinates:
 C17(H17)
3.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B)
3.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16)
3.d Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C)
;
_shelx_res_checksum              45538
_olex2_date_sample_completion    2021-01-17
_olex2_date_sample_data_collection 2021-01-11
_olex2_date_sample_submission    2021-01-11
_olex2_exptl_crystal_mounting_method 'mounted on a nylon loop with Krytox oil'
_olex2_submission_original_sample_id CDS-5-62
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 7.634
_oxdiff_exptl_absorpt_empirical_full_min 0.291