Mechanistic insights into boron-catalysed direct amidation reactions.
Arkhipenko, Sergey; Sabatini, Marco T.; Batsanov, Andrei S.; Karaluka, Valerija; Sheppard, Tom D.; Rzepa, Henry S.; Whiting, Andrew; Chemical science 9 (2018) 1058–1072; doi:10.1039/c7sc03595k

data_1548576
_publ_section_title
;
 Mechanistic insights into boron-catalysed direct amidation reactions.
;
_journal_issue                   4
_journal_name_full               'Chemical science'
_journal_page_first              1058
_journal_page_last               1072
_journal_paper_doi               10.1039/c7sc03595k
_journal_volume                  9
_journal_year                    2018
_chemical_formula_moiety         'C32 H33 B3 N2 O3, 2(C7 H9 N)'
_chemical_formula_sum            'C46 H51 B3 N4 O3'
_chemical_formula_weight         740.33
_chemical_melting_point          329.4(3)
_chemical_name_systematic
'phenylboroxine complex with 4 equiv. benzylamine '
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-02-15
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_audit_update_record
;
2017-07-17 deposited with the CCDC.
2018-01-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.8857(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.2120(9)
_cell_length_b                   11.2705(5)
_cell_length_c                   18.8494(8)
_cell_measurement_reflns_used    9868
_cell_measurement_temperature    120
_cell_measurement_theta_max      26.839
_cell_measurement_theta_min      2.18
_cell_volume                     4087.9(3)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2016)'
_computing_data_collection       'APEX3 v.2016.1_0 (Bruker, 2016)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS 2013/1 (Sheldrick, 2008)'
_diffrn_ambient_temperature      120.0
_diffrn_detector_area_resol_mean 10.4
_diffrn_detector_type            'Bruker PHOTON 100 CMOS'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       '3-circle area detector diffractometer'
_diffrn_measurement_device_type  D8V
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'focusing mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0559
_diffrn_reflns_av_unetI/netI     0.0335
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            68095
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.998
_diffrn_reflns_theta_max         25.998
_diffrn_reflns_theta_min         2.117
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\mS microsource'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.074
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9421
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker, 2014) was used for absorption correction.
wR2(int) was 0.1307 before and 0.0620 after correction.
The Ratio of minimum to maximum transmission is 0.9421.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.203
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1576
_exptl_crystal_size_max          0.294
_exptl_crystal_size_mid          0.164
_exptl_crystal_size_min          0.128
_refine_diff_density_max         0.307
_refine_diff_density_min         -0.276
_refine_diff_density_rms         0.038
_refine_ls_extinction_coef       0.0039(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014)'
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     584
_refine_ls_number_reflns         8022
_refine_ls_number_restraints     604
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0740
_refine_ls_R_factor_gt           0.0496
_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^)+(0.0380P)^2^+2.5270P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1053
_refine_ls_wR_factor_ref         0.1169
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6020
_reflns_number_total             8022
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc03595k2.cif
_cod_data_source_block           10d_16srv262
_cod_depositor_comments
;
The following automatic conversions were performed:

'_diffrn_radiation_probe' value 'X-ray' changed to 'x-ray' according
to
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 

 Adding full bibliography for 1548566--1548579.cif.
;
_cod_database_code               1548576
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.979
_computing.bruker_data_scaling   'SADABS V2014/5 (Bruker AXS Inc.)'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C2-C3B \\sim C2-C7B \\sim C4B-C3B \\sim C4A-C3A \\sim C5A-C4A \\sim C5B-C4B
\\sim C6B-C5B \\sim C6A-C5A ~
 C7A-C6A \\sim C7B-C6B \\sim C2-C3A \\sim C2-C7A
 with sigma of 0.02
 C40B-C35B \\sim C40A-C35A \\sim C40B-C39B \\sim C40A-C39A \\sim C39B-C38B
\\sim C39A-C38A \\sim C38B-
 C37B \\sim C38A-C37A \\sim C37A-C36A \\sim C37B-C36B \\sim C36B-C35B \\sim
C36A-C35A
 with sigma of 0.02
 C35B-C34 \\sim C35A-C34
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C35B) = Uanis(C35A)
Uanis(C7A) = Uanis(C7B)
Uanis(C6A) = Uanis(C6B)
Uanis(C5A) = Uanis(C5B)
Uanis(C4A) = Uanis(C4B)
Uanis(C3A) = Uanis(C3B)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: C3A(0.5) H3A(0.5) C4A(0.5) H4A(0.5) C5A(0.5) H5A(0.5) C6A(0.5)
 H6A(0.5) C7A(0.5) H7A(0.5) C3B(0.5) H3B(0.5) C4B(0.5) H4B(0.5) C5B(0.5)
 H5B(0.5) C6B(0.5) H6B(0.5) C7B(0.5) H7B(0.5) C35A(0.7) C36A(0.7) H36A(0.7)
 C37A(0.7) H37A(0.7) C38A(0.7) H38A(0.7) C39A(0.7) H39A(0.7) C40A(0.7)
 H40A(0.7) C35B(0.3) C36B(0.3) H36B(0.3) C37B(0.3) H37B(0.3) C38B(0.3)
 H38B(0.3) C39B(0.3) H39B(0.3) C40B(0.3) H40B(0.3)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1C,H1D), C14(H14A,H14B), C41(H41A,H41B)
6.b Aromatic/amide H refined with riding coordinates:
 C3A(H3A), C4A(H4A), C5A(H5A), C6A(H6A), C7A(H7A), C3B(H3B), C4B(H4B),
 C5B(H5B), C6B(H6B), C7B(H7B), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13),
 C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C22(H22), C23(H23), C24(H24),
  C25(H25), C26(H26), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32),
 C36A(H36A), C37A(H37A), C38A(H38A), C39A(H39A), C40A(H40A), C36B(H36B),
 C37B(H37B), C38B(H38B), C39B(H39B), C40B(H40B), C43(H43), C44(H44), C45(H45),
 C46(H46), C47(H47)
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_shelx_res_checksum              12788