anti-Selective synthesis of β-boryl-α-amino acid derivatives by Cu-catalysed borylamination of α,β-unsaturated esters
Hirano, Koji; Nishino, Soshi; Nishii, Yuji; Chemical Science  (2022) –; doi:10.1039/D2SC06003E

data_1568012
_publ_section_title
;
 &#x000D; anti-Selective synthesis of \b-boryl-\a-amino acid derivatives
 by Cu-catalysed borylamination of \a,\b-unsaturated esters
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC06003E
_journal_year                    2022
_chemical_formula_moiety         'C25 H34 B N O4'
_chemical_formula_sum            'C25 H34 B N O4'
_chemical_formula_weight         423.34
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-09-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-09-09 deposited with the CCDC.	2022-11-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.311(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.4689(2)
_cell_length_b                   20.7919(4)
_cell_length_c                   12.8601(3)
_cell_measurement_reflns_used    10367
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      73.9560
_cell_measurement_theta_min      4.2100
_cell_volume                     2389.40(9)
_computing_cell_refinement       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.990
_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     66.00  91.00   0.50    0.05    --   42.80 133.00 -77.00   50
  2  \w     84.00 109.00   0.50    0.05    --   76.50 133.00 -77.00   50
  3  \w     78.00 115.00   0.50    0.05    --   42.80 125.00-180.00   74
  4  \w     65.00  90.00   0.50    0.05    --   42.80 136.00 100.00   50
  5  \w     90.00 116.00   0.50    0.05    --   76.50 136.00 100.00   52
  6  \w    -69.00 -31.00   0.50    0.05    -- -106.00  37.00 -30.00   76
  7  \w   -101.00 -19.00   0.50    0.05    --  -42.80 133.00 -77.00  164
  8  \w    -83.00 -57.00   0.50    0.05    -- -106.00 125.00-150.00   52
  9  \w   -104.00 -59.00   0.50    0.05    -- -106.00 133.00 -77.00   90
 10  \w   -111.00 -34.00   0.50    0.05    -- -106.00 125.00-120.00  154
 11  \w   -114.00 -33.00   0.50    0.05    -- -106.00 125.00 -90.00  162
 12  \w    -86.00 -41.00   0.50    0.05    -- -106.00 125.00  30.00   90
 13  \w    -97.00 -71.00   0.50    0.05    -- -106.00 125.00 120.00   52
 14  \w   -117.00 -80.00   0.50    0.05    -- -106.00 136.00 100.00   74
 15  \w   -117.00 -42.00   0.50    0.05    -- -106.00 125.00  90.00  150
 16  \w    -80.00 -32.00   0.50    0.05    -- -106.00  57.00 150.00   96
 17  \w    -84.00 -59.00   0.50    0.05    --  -42.80 136.00 100.00   50
 18  \w     44.00  69.00   0.50    0.05    --   76.50-133.00-145.00   50
 19  \w   -115.00 -17.00   0.50    0.05    --  -42.80 -77.00-150.00  196
 20  \w   -109.00 -71.00   0.50    0.05    --  -42.80-125.00   0.00   76
 21  \w   -145.00-120.00   0.50    0.05    -- -106.00-133.00-145.00   50
 22  \w   -177.00-135.00   0.50    0.05    -- -106.00 -37.00 -60.00   84
 23  \w   -159.00 -83.00   0.50    0.05    -- -106.00 -19.00  30.00  152
 24  \w   -125.00 -77.00   0.50    0.05    -- -106.00  37.00 -30.00   96
 25  \w   -113.00 -87.00   0.50    0.05    -- -106.00 125.00  30.00   52
 26  \w   -128.00-102.00   0.50    0.05    -- -106.00  57.00 150.00   52
 27  \w   -108.00 -71.00   0.50    0.05    --  -42.80-125.00 150.00   74
 28  \w   -144.00-119.00   0.50    0.05    -- -106.00-136.00  36.00   50
 29  \w   -169.00 -71.00   0.50    0.05    -- -106.00-125.00   0.00  196
 30  \w   -173.00 -86.00   0.50    0.05    -- -106.00 -37.00-180.00  174
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0641131000
_diffrn_orient_matrix_UB_12      -0.0271120000
_diffrn_orient_matrix_UB_13      -0.1177857000
_diffrn_orient_matrix_UB_21      0.0274141000
_diffrn_orient_matrix_UB_22      -0.0689383000
_diffrn_orient_matrix_UB_23      0.0461874000
_diffrn_orient_matrix_UB_31      -0.1577338000
_diffrn_orient_matrix_UB_32      -0.0009810000
_diffrn_orient_matrix_UB_33      0.0099996000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0354
_diffrn_reflns_av_unetI/netI     0.0252
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            20729
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.059
_diffrn_reflns_theta_min         4.218
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.619
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77825
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.43a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.177
_exptl_crystal_description       prism
_exptl_crystal_F_000             912
_exptl_crystal_size_max          0.92
_exptl_crystal_size_mid          0.632
_exptl_crystal_size_min          0.397
_refine_diff_density_max         0.214
_refine_diff_density_min         -0.334
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     286
_refine_ls_number_reflns         4808
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0493
_refine_ls_R_factor_gt           0.0462
_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^)+(0.0612P)^2^+0.8515P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1198
_refine_ls_wR_factor_ref         0.1221
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4423
_reflns_number_total             4808
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc06003e2.cif
_cod_data_source_block           nishino_210608
_cod_database_code               1568012
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C25 H35 N B O4'
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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:
 C9(H9), C14(H14)
2.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C7(H7A,H7B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C18(H18), C22(H22), C2(H2), C4(H4), C19(H19), C5(H5), C20(H20),
 C3(H3), C21(H21)
2.d Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C15(H15A,H15B,H15C), C12(H12A,H12B,H12C), C30(H30A,H30B,
 H30C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C)
;
_shelx_res_checksum              93871
_shelx_hkl_checksum              88312
_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 1.388
_oxdiff_exptl_absorpt_empirical_full_min 0.682