Synthesis of Chiral α-Amino Tertiary Boronates via the Catalytic Enantioselective Nucleophilic Borylation of Dialkyl Ketimines
Kubota, Koji; Miura, Daiyo; Takeuchi, Takumi; Osaki, Shun; Ito, Hajime; ACS Catalysis  (2021) 6733–6740; doi:10.1021/acscatal.1c01689

data_4518739
_publ_section_title
;
 Synthesis of Chiral \a-Amino Tertiary Boronates via the Catalytic
 Enantioselective Nucleophilic Borylation of Dialkyl Ketimines
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              6733
_journal_page_last               6740
_journal_paper_doi               10.1021/acscatal.1c01689
_journal_year                    2021
_chemical_absolute_configuration syn
_chemical_formula_moiety         '2(C26 H39 B N O3 P)'
_chemical_formula_sum            'C52 H78 B2 N2 O6 P2'
_chemical_formula_weight         910.72
_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             2020-12-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 111.6360(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.83470(10)
_cell_length_b                   33.8529(3)
_cell_length_c                   10.56040(10)
_cell_measurement_reflns_used    10259
_cell_measurement_temperature    123
_cell_measurement_theta_max      73.3000
_cell_measurement_theta_min      4.6680
_cell_volume                     2603.57(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.43a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.43a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.43a (Rigaku OD, 2018)'
_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      123
_diffrn_detector                 'PLATUS 200K area detector'
_diffrn_detector_area_resol_mean 5.811
_diffrn_detector_type            'HPC area detector'
_diffrn_measured_fraction_theta_full 0.941
_diffrn_measured_fraction_theta_max 0.910
_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    -18.00   9.00   0.50    3.89    --    5.00  43.00   3.00   54
  2  \w    -83.00  26.00   0.50    3.89    --    5.00  52.00 148.00  218
  3  \w   -182.00-157.00   0.50    3.89    --  -96.30  43.00   3.00   50
  4  \w    -95.00 -48.00   0.50    3.89    --  -96.30  52.00 148.00   94
  5  \w     10.00  38.00   0.50    3.89    --    5.00  43.00   3.00   56
  6  \w    -89.00  -9.00   0.50    3.89    --  -96.30  43.00-120.00  160
  7  \w   -186.00-107.00   0.50    3.89    --  -96.30  29.00-150.00  158
  8  \w    -86.00 -11.00   0.50    3.89    --  -96.30  29.00-150.00  150
  9  \w   -180.00  -7.00   0.50    3.89    --  -96.30  43.00  30.00  346
 10  \w   -180.00-134.00   0.50    3.89    --  -96.30  43.00-120.00   92
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB P200'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0804474000
_diffrn_orient_matrix_UB_12      0.0184694000
_diffrn_orient_matrix_UB_13      0.1431896000
_diffrn_orient_matrix_UB_21      -0.1559717000
_diffrn_orient_matrix_UB_22      0.0307356000
_diffrn_orient_matrix_UB_23      -0.0414976000
_diffrn_orient_matrix_UB_31      -0.1181170000
_diffrn_orient_matrix_UB_32      -0.0280119000
_diffrn_orient_matrix_UB_33      0.0489092000
_diffrn_radiation_monochromator  'multi-layer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0223
_diffrn_reflns_av_unetI/netI     0.0268
_diffrn_reflns_Laue_measured_fraction_full 0.941
_diffrn_reflns_Laue_measured_fraction_max 0.910
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_k_min       -41
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            12604
_diffrn_reflns_point_group_measured_fraction_full 0.791
_diffrn_reflns_point_group_measured_fraction_max 0.752
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.768
_diffrn_reflns_theta_min         4.690
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_type              micromax007
_exptl_absorpt_coefficient_mu    1.132
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57721
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.43a (Rigaku Oxford Diffraction, 2018)
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    1.162
_exptl_crystal_description       block
_exptl_crystal_F_000             984
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.229
_refine_diff_density_min         -0.244
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 2815 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.075(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.109
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     701
_refine_ls_number_reflns         7917
_refine_ls_number_restraints     349
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0332
_refine_ls_R_factor_gt           0.0324
_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^)+(0.0649P)^2^+0.0744P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0931
_refine_ls_wR_factor_ref         0.0939
_reflns_Friedel_coverage         0.625
_reflns_Friedel_fraction_full    0.635
_reflns_Friedel_fraction_max     0.589
_reflns_number_gt                7650
_reflns_number_total             7917
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c01689_si_002.cif
_cod_data_source_block           mur_20200210
_cod_database_code               4518739
_shelx_shelxl_version_number     2018/1
_reflns_odcompleteness_completeness 94.15
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
C00E \\sim C01O \\sim C01B \\sim C01N \\sim C01I \\sim C00H: within 1.7A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C01L \\sim C01Q \\sim C01P \\sim C01M \\sim C00O \\sim C010: within 1.7A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C00H \\sim C00E \\sim C01O \\sim C01B \\sim C01N \\sim C01I \\sim C1: within
1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C1A \\sim C0AA \\sim C1AA \\sim C2AA \\sim C3AA \\sim C4AA \\sim C5AA: within
1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C01R \\sim C01M \\sim C00O \\sim C010 \\sim C01L \\sim C01Q \\sim C01P: within
1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C6AA \\sim C0 \\sim C7AA \\sim C8AA \\sim C9AA \\sim C0BA \\sim C01S: within
1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
3. Rigid body (RIGU) restrains
 C01I, C01N, C01B, C01O, C00E, C00H
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C01L, C01Q, C01P, C01M, C00O, C010
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C00H, C00E, C01O, C01B, C01N, C01I, C1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1A, C0AA, C1AA, C2AA, C3AA, C4AA, C5AA
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C01M, C00O, C010, C01L, C01Q, C01P, C01R
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C01S, C0BA, C6AA, C0, C7AA, C8AA, C9AA
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Fixed Sof: C00H(0.5) H00L(0.5) C00E(0.5) C01O(0.5) C01B(0.5) H01Z(0.5)
 C01N(0.5) H01(0.5) C01I(0.5) H0AA(0.5) C01M(0.5) C00O(0.5) C010(0.5) H010(0.5)
 C01L(0.5) H01S(0.5) C01Q(0.5) H01T(0.5) C01P(0.5) H01U(0.5) C01R(0.5)
 H01V(0.5) H01W(0.5) H01X(0.5) C1(0.5) H1A(0.5) H1B(0.5) H1C(0.5) C1A(0.5)
 H1AB(0.5) H1AC(0.5) H1AD(0.5) C0AA(0.5) C1AA(0.5) H1AE(0.5) C2AA(0.5)
 H2AB(0.5) C3AA(0.5) H3AB(0.5) C4AA(0.5) H4AB(0.5) C5AA(0.5) C6AA(0.5) C0(0.5)
 H0(0.5) C7AA(0.5) H7AA(0.5) C8AA(0.5) H8AA(0.5) C9AA(0.5) H9AA(0.5) C0BA(0.5)
 C01S(0.5) H01Y(0.5) HN(0.5) HO(0.5)
5.a Riding coordinates:
 N009(H009)
5.b Aromatic/amide H refined with riding coordinates:
 N00A(H00K), C00C(H00C), C00H(H00L), C01B(H01Z), C01N(H01), C01I(H0AA),
 C00M(H00M), C00P(H00P), C00Q(H00Q), C00V(H00V), C011(H011), C012(H012),
 C018(H018), C010(H010), C01L(H01S), C01Q(H01T), C01P(H01U), C1AA(H1AE),
 C2AA(H2AB), C3AA(H3AB), C4AA(H4AB), C0(H0), C7AA(H7AA), C8AA(H8AA), C9AA(H9AA)
5.c Fitted hexagon refined as free rotating group:
 C00H(C00E,C01O,C01B,C01N,C01I), C01M(C00O,C010,C01L,C01Q,C01P)
5.d Idealised Me refined as rotating group:
 C00G(H00A,H00B,H00D), C00S(H00N,H00O,H00R), C00T(H00E,H00F,H00G), C00X(H00S,
 H00T,H00U), C00Y(H00H,H00I,H00J), C013(H1AA,H,HA), C014(H01A,H01B,H01C),
 C016(H01D,H01E,H01F), C017(H01G,H01H,H01I), C019(H01J,H01K,H01L), C01A(H2AA,HB,
 HC), C01C(H3AA,HD,HE), C01D(H4AA,HF,HG), C01E(H01M,H01N,H01O), C01F(H5AA,HH,
 HI), C01H(H6AA,HJ,HK), C01J(H0BA,HL,HM), C01K(H01P,H01Q,H01R), C01R(H01V,H01W,
 H01X), C1(H1A,H1B,H1C), C1A(H1AB,H1AC,H1AD), C01S(H01Y,HN,HO)
;
_shelx_res_checksum              55881
_shelx_hkl_checksum              37948
_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 1.733
_oxdiff_exptl_absorpt_empirical_full_min 0.658