One-step synthesis of chiral multifluorine-substituted-alkoxy boranils using H3BO3 as boron source
Han, Shumi; Dou, Yingchao; Niu, Jun-Long; Organic & Biomolecular Chemistry  (2025) –; doi:10.1039/D5OB01781E

data_7160923
_publ_section_title
;
 One-step synthesis of chiral multifluorine-substituted-alkoxy boranils
 using H3BO3 as boron source
;
_journal_name_full               'Organic &amp; Biomolecular Chemistry'
_journal_paper_doi               10.1039/D5OB01781E
_journal_year                    2025
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C48 H56 B2 F24 N2 O6'
_chemical_formula_sum            'C48 H56 B2 F24 N2 O6'
_chemical_formula_weight         1234.56
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_block_doi                 10.5517/ccdc.csd.cc2pxr4j
_audit_creation_date             2025-09-17
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-11-04 deposited with the CCDC.	2025-12-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.233(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.6425(8)
_cell_length_b                   13.8768(8)
_cell_length_c                   36.1840(14)
_cell_measurement_reflns_used    9305
_cell_measurement_temperature    293.00
_cell_measurement_theta_max      25.23
_cell_measurement_theta_min      2.35
_cell_volume                     11506.9(9)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      293.00
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0786
_diffrn_reflns_av_unetI/netI     0.0357
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            181831
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         1.880
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.144
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6539
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1541 before and 0.0730 after correction.
The Ratio of minimum to maximum transmission is 0.8770.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.425
_exptl_crystal_description       block
_exptl_crystal_F_000             5056
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.441
_refine_diff_density_min         -0.323
_refine_diff_density_rms         0.080
_refine_ls_abs_structure_details
;
 Flack x determined using 4875 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.0(2)
_refine_ls_extinction_coef       0.0138(14)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.232
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1658
_refine_ls_number_reflns         19998
_refine_ls_number_restraints     790
_refine_ls_restrained_S_all      1.231
_refine_ls_R_factor_all          0.1320
_refine_ls_R_factor_gt           0.0960
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2687
_refine_ls_wR_factor_ref         0.3352
_reflns_Friedel_coverage         0.907
_reflns_Friedel_fraction_full    0.979
_reflns_Friedel_fraction_max     0.979
_reflns_number_gt                12495
_reflns_number_total             19998
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01781e2.cif
_cod_data_source_block           20240919hsm2_a
_cod_database_code               7160923
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.972
_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
 F3A-C99 = F1A-C99 = F2A-C99 = F50-C2A = F51-C2A = F49-C2A
 1.31 with sigma of 0.01
 F3A-C73
 2.329 with sigma of 0.01
 F49-C73
 2.329 with sigma of 0.01
 F2A-C73
 2.329 with sigma of 0.01
 C99-C73 = C2A-C73
 1.53 with sigma of 0.01
 F51-C73
 2.329 with sigma of 0.01
 F1A-C73
 2.329 with sigma of 0.01
 F50-C73
 2.329 with sigma of 0.01
 C75-C73 = C74-C73
 1.53 with sigma of 0.01
 C70-C72 = C70-C71 = C74-C73 = C75-C73 = C62-C59 = C60-C59 = C59-C57 = C61-C59
 = C51-C52 = C50-C52 = C49-C52 = C69-C64 = C68-C69 = C67-C68 = C67-C66 = C65-
 C64 = C66-C65 = C81-C79 = C80-C79 = C94-C93 = C95-C93 = C96-C93 = C91-C89 =
 C92-C89 = C90-C89 = C85-C93 = C89-C87 = C52-C53 = C77-C76 = C78-C76 = C35-C33 =
  C36-C35 = C37-C35 = C38-C35 = C9-C11 = C13-C11 = C12-C11 = C14-C11 = C2-C5 =
 C1-C2 = C4-C2 = C3-C2 = C22-C23 = C22-C27 = C26-C27 = C26-C25 = C25-C24 = C23-
 C24 = C41-C39 = C31-C39 = C40-C39 = C42-C39 = C44-C43 = C45-C43 = C48-C46 =
 C47-C46 = C19-C21 = C20-C19 = C17-C16 = C18-C16
 1.53 with sigma of 0.001
 C89-C91 \\sim C89-C04J
 with sigma of 0.02
 C89-C90 \\sim C89-C1A
 with sigma of 0.02
 C89-C92 \\sim C89-C98
 with sigma of 0.02
 C52-C49 \\sim C52-C0
 with sigma of 0.02
 C35-C37 \\sim C35-C04L
 with sigma of 0.02
 C52-C51 \\sim C52-C100
 with sigma of 0.02
 C2-C1 \\sim C2-C103
 with sigma of 0.02
 F51-F49 \\sim F41-F42
 with sigma of 0.04
 C2-C3 \\sim C2-C04F
 with sigma of 0.02
 C73-F3A \\sim C73-F37
 with sigma of 0.04
 F49-F50 \\sim F42-F40
 with sigma of 0.04
 C2-C4 \\sim C2-C102
 with sigma of 0.02
 C35-C38 \\sim C35-C03{
 with sigma of 0.02
 F1A-F3A \\sim F38-F37
 with sigma of 0.04
 C73-C2A \\sim C73-C75
 with sigma of 0.02
 C52-C50 \\sim C52-C04D
 with sigma of 0.02
 F1A-C99 \\sim F38-C74
 with sigma of 0.02
 C35-C36 \\sim C35-C101
 with sigma of 0.02
 F2A-F3A \\sim F39-F37
 with sigma of 0.04
 F51-C2A \\sim F41-C75
 with sigma of 0.02
 C73-C99 \\sim C73-C74
 with sigma of 0.02
 F2A-C99 \\sim F39-C74
 with sigma of 0.02
 C73-F50 \\sim C73-F40
 with sigma of 0.04
 F1A-F2A \\sim F38-F39
 with sigma of 0.04
 F49-C2A \\sim F42-C75
 with sigma of 0.02
 F51-F50 \\sim F41-F40
 with sigma of 0.04
 F50-C2A \\sim F40-C75
 with sigma of 0.02
 C99-F3A \\sim C74-F37
 with sigma of 0.02
 C73-F1A \\sim C73-F38
 with sigma of 0.04
 C73-F51 \\sim C73-F41
 with sigma of 0.04
 C73-F2A \\sim C73-F39
 with sigma of 0.04
 C73-F49 \\sim C73-F42
 with sigma of 0.04
 F49-F50 \\sim F49-F51 \\sim F50-F51
 with sigma of 0.02
 F40-F42 \\sim F40-F41 \\sim F42-F41
 with sigma of 0.02
 C39-C41 \\sim C39-C97
 with sigma of 0.02
 C39-C42 \\sim C39-C105
 with sigma of 0.02
 C39-C40 \\sim C39-C104
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C73 \\sim F1A \\sim F51 \\sim F2A \\sim F49 \\sim F50 \\sim C99 \\sim C2A \\sim
F3A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C89 \\sim C92 \\sim C90 \\sim C91 \\sim C98 \\sim C04J \\sim C1A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C51 \\sim C100 \\sim C52 \\sim C04D \\sim C50 \\sim C49 \\sim C0: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C102 \\sim C4 \\sim C2 \\sim C1 \\sim C103 \\sim C3 \\sim C04F: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C04L \\sim C37 \\sim C35 \\sim C38 \\sim C03{ \\sim C36 \\sim C101: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C73 \\sim F1A \\sim F51 \\sim F2A \\sim F49 \\sim F50 \\sim C99 \\sim C2A \\sim
F3A \\sim F38 \\sim F41 \\sim F39 \\sim F42 \\sim F40 \\sim C74 \\sim C75 \\sim
F37: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C39 \\sim C42 \\sim C41 \\sim C105 \\sim C97 \\sim C40 \\sim C104: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 C73, F1A, F51, F2A, F49, F50, C99, C2A, F3A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C73, F1A, F51, F2A, F49, F50, C99, C2A, F3A, F38, F41, F39, F42, F40, C74,
 C75, F37
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Sof(H73)=Sof(F38)=Sof(F41)=Sof(F39)=Sof(F42)=Sof(F40)=Sof(C74)=Sof(C75)=
 Sof(F37)=1-FVAR(1)
 Sof(HB)=Sof(F1A)=Sof(F51)=Sof(F2A)=Sof(F49)=Sof(F50)=Sof(C99)=Sof(C2A)=
 Sof(F3A)=FVAR(1)
 Sof(C98)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C04J)=Sof(H7)=Sof(HS)=Sof(HT)=
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=1-FVAR(2)
 Sof(C92)=Sof(H92A)=Sof(H92B)=Sof(H92C)=Sof(C90)=Sof(H90A)=Sof(H90B)=Sof(H90C)=
 Sof(C91)=Sof(H91A)=Sof(H91B)=Sof(H91C)=FVAR(2)
 Sof(C0)=Sof(H0A)=Sof(H0B)=Sof(H0C)=Sof(C04D)=Sof(H8)=Sof(HU)=Sof(HV)=
 Sof(C100)=Sof(H1)=Sof(H2)=Sof(H3)=1-FVAR(3)
 Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=FVAR(3)
 Sof(C101)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C04L)=Sof(H04Z)=Sof(HW)=Sof(HX)=
 Sof(C03{)=Sof(H03J)=Sof(H03K)=Sof(H03L)=1-FVAR(4)
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=FVAR(4)
 Sof(C102)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C04F)=Sof(H04)=Sof(HY)=Sof(HZ)=
 Sof(C103)=Sof(H7A)=Sof(H7B)=Sof(H7C)=1-FVAR(5)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C4)=
 Sof(H4A)=Sof(H4B)=Sof(H4C)=FVAR(5)
 Sof(C104)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C105)=Sof(H9A)=Sof(H9B)=Sof(H9C)=
 Sof(C97)=Sof(H10A)=Sof(H10B)=Sof(H10C)=1-FVAR(6)
 Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=
 Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=FVAR(6)
6.a Riding coordinates:
 C38(H38A,H38B,H38C), C49(H49A,H49B,H49C), C1(H1A,H1B,H1C), C36(H36A,H36B,
 H36C), C92(H92A,H92B,H92C), C50(H50A,H50B,H50C), C90(H90A,H90B,H90C), C3(H3A,
 H3B,H3C), C51(H51A,H51B,H51C), C4(H4A,H4B,H4C), C91(H91A,H91B,H91C), C37(H37A,
 H37B,H37C), C98(H2A,H2B,H2C), C04J(H7,HS,HT), C1A(H1AA,H1AB,H1AC), C0(H0A,H0B,
 H0C), C04D(H8,HU,HV), C100(H1,H2,H3), C101(H5A,H5B,H5C), C04L(H04Z,HW,HX),
 C03{(H03J,H03K,H03L), C102(H6A,H6B,H6C), C04F(H04,HY,HZ), C103(H7A,H7B,H7C)
6.b Ternary CH refined with riding coordinates:
 C64(H64), C65(H65), C76(H76), C27(H27), C22(H22), C16(H16), C79(H79),
 C46(H46), C19(H19), C43(H43), C70(H70), C73(HB), C73(H73)
6.c Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C25(H25A,H25B), C66(H66A,H66B), C69(H69A,H69B), C23(H23A,
 H23B), C26(H26A,H26B), C68(H68A,H68B), C67(H67A,H67B)
6.d Aromatic/amide H refined with riding coordinates:
 C10(H10), C6(H6), C82(H82), C15(H15), C63(H63), C28(H28), C88(H88), C86(H86),
 C54(H54), C58(H58), C34(H34), C32(H32)
6.e Fitted hexagon refined as free rotating group:
 C7(C8,C9,C10,C5,C6), C88(C87,C86,C85,C84,C83), C53(C54,C55,C56,C57,C58),
 C30(C29,C34,C33,C32,C31)
6.f Idealised Me refined as rotating group:
 C62(H62A,H62B,H62C), C95(H95A,H95B,H95C), C60(H60A,H60B,H60C), C96(H96A,H96B,
 H96C), C40(H40A,H40B,H40C), C94(H94A,H94B,H94C), C13(H13A,H13B,H13C), C12(H12A,
 H12B,H12C), C42(H42A,H42B,H42C), C61(H61A,H61B,H61C), C41(H41A,H41B,H41C),
 C14(H14A,H14B,H14C), C104(H8A,H8B,H8C), C105(H9A,H9B,H9C), C97(H10A,H10B,H10C)
;
_shelx_res_checksum              17867
_shelx_hkl_checksum              5054
_olex2_submission_special_instructions 'No special instructions were received'