Synthesis of isoxazoloazaborines via gold(i)-catalyzed propargyl aza-Claisen rearrangement/borylative cyclization cascade
Tsuda, Masato; Morita, Taiki; Nakamura, Hiroyuki; Chemical Communications  (2022) –; doi:10.1039/D1CC07002A

data_7129592
_publ_section_title
;
 Synthesis of isoxazoloazaborines via gold(i)-catalyzed propargyl
 aza-Claisen rearrangement/borylative cyclization cascade
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC07002A
_journal_year                    2022
_chemical_formula_moiety
'7(C22 H22 B Cl N2 O Si), C22 H20 B Cl N2 O Si'
_chemical_formula_sum            'C176 H174 B8 Cl8 N16 O8 Si8'
_chemical_formula_weight         3236.10
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-10-26
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2021-10-28 deposited with the CCDC.	2022-01-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.467(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   29.3806(10)
_cell_length_b                   23.8849(6)
_cell_length_c                   25.2367(9)
_cell_measurement_reflns_used    22939
_cell_measurement_temperature    90
_cell_measurement_theta_max      74.7210
_cell_measurement_theta_min      3.1750
_cell_volume                     16983.5(10)
_computing_cell_refinement       'CrysAlisPro 1.171.41.114a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.114a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.114a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      90
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.976
_diffrn_measured_fraction_theta_max 0.927
_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   -103.00 -77.00   0.50    2.00    --  -47.88 -47.00-162.00   52
  2  \w    -36.00  18.00   0.50    2.00    --  -47.88  47.00 -13.00  108
  3  \w     39.00 118.00   0.50    2.00    --   47.88  47.00 -13.00  158
  4  \w    -23.00  31.00   0.50    2.00    --   47.88 -47.00-162.00  108
  5  \w   -157.00-132.00   0.50    3.00    -- -102.00 -47.00-162.00   50
  6  \w    102.00 176.00   0.50    3.00    --  103.68  47.00 -13.00  148
  7  \w    -18.00  23.00   0.50    2.00    --  -47.88  19.00  90.00   82
  8  \w   -117.00 -76.00   0.50    2.00    --  -47.88-125.00   0.00   82
  9  \w     -9.00  23.00   0.50    2.00    --   47.88 -19.00  30.00   64
 10  \w   -175.00-105.00   0.50    3.00    -- -102.00 -19.00 -90.00  140
 11  \w    -63.00 -31.00   0.50    3.00    -- -102.00  57.00 -30.00   64
 12  \w    -63.00 -31.00   0.50    3.00    -- -102.00  57.00-150.00   64
 13  \w    -64.00 -31.00   0.50    3.00    -- -102.00  57.00 120.00   66
 14  \w    -64.00 -30.00   0.50    3.00    -- -102.00  57.00-180.00   68
 15  \w   -123.00 -87.00   0.50    3.00    -- -102.00  77.00  90.00   72
 16  \w    -68.00 -34.00   0.50    3.00    -- -102.00 125.00   0.00   68
 17  \w    -60.00 -31.00   0.50    3.00    -- -102.00  57.00  30.00   58
 18  \w   -112.00 -81.00   0.50    3.00    -- -102.00  77.00 -90.00   62
 19  \w    -55.00 -30.00   0.50    3.00    -- -102.00  77.00 -90.00   50
 20  \w    -61.00 -34.00   0.50    3.00    -- -102.00  57.00  90.00   54
 21  \w    -63.00 -35.00   0.50    3.00    -- -102.00  57.00 150.00   56
 22  \w    -61.00 -31.00   0.50    3.00    -- -102.00  57.00   0.00   60
 23  \w     32.00 107.00   0.50    3.00    --  103.68-125.00 150.00  150
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0497015000
_diffrn_orient_matrix_UB_12      0.0012764000
_diffrn_orient_matrix_UB_13      -0.0090191000
_diffrn_orient_matrix_UB_21      0.0191488000
_diffrn_orient_matrix_UB_22      -0.0371765000
_diffrn_orient_matrix_UB_23      0.0513590000
_diffrn_orient_matrix_UB_31      -0.0122766000
_diffrn_orient_matrix_UB_32      -0.0526692000
_diffrn_orient_matrix_UB_33      -0.0365140000
_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  0.0563
_diffrn_reflns_av_unetI/netI     0.0557
_diffrn_reflns_Laue_measured_fraction_full 0.976
_diffrn_reflns_Laue_measured_fraction_max 0.927
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            114522
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.927
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.618
_diffrn_reflns_theta_min         2.425
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.241
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72351
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.114a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.266
_exptl_crystal_description       block
_exptl_crystal_F_000             6776
_exptl_crystal_size_max          0.243
_exptl_crystal_size_mid          0.055
_exptl_crystal_size_min          0.044
_refine_diff_density_max         2.382
_refine_diff_density_min         -0.543
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2041
_refine_ls_number_reflns         33108
_refine_ls_number_restraints     2819
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.1005
_refine_ls_R_factor_gt           0.0693
_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^)+(0.0760P)^2^+25.8130P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1733
_refine_ls_wR_factor_ref         0.1901
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23086
_reflns_number_total             33108
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc07002a2.cif
_cod_data_source_block           crl421362-2_auto
_cod_original_cell_volume        16983.4(10)
_cod_database_code               7129592
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.908
_shelx_estimated_absorpt_t_min   0.612
_reflns_odcompleteness_completeness 97.59
_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 C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Si9-C34 \\sim Si9A-C34
 with sigma of 0.02
 Si9-C231 \\sim Si9A-C1
 with sigma of 0.02
 Si9-C230 \\sim Si9A-C2
 with sigma of 0.02
 Si9-C232 \\sim Si9A-C3
 with sigma of 0.02
 C231-C230 \\sim C1-C2
 with sigma of 0.04
 C230-C232 \\sim C2-C3
 with sigma of 0.04
 C34-C232 \\sim C34-C3
 with sigma of 0.04
 C231-C232 \\sim C1-C3
 with sigma of 0.04
 C34-C231 \\sim C34-C1
 with sigma of 0.04
 C34-C230 \\sim C34-C2
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.01 and sigma
for terminal atoms of 0.02
4. Others
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(Si9A)=Sof(C1)=Sof(H1A)=Sof(H1B)=
 Sof(H1C)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=1-FVAR(1)
 Sof(Si9)=Sof(C231)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C230)=Sof(H23D)=
 Sof(H23E)=Sof(H23F)=Sof(C232)=Sof(H23G)=Sof(H23H)=Sof(H23I)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 N61(H61), N172(H172), N89(H89), N144(H144), N31(H31), N117(H117), N3(H3),
 N201(H201), C15(H15), C187(H187), C160(H160), C14(H14), C191(H191), C159(H159),
  C17(H17), C55(H55), C69(H69), C40(H40), C125(H125), C188(H188), C128(H128),
 C73(H73), C39(H39), C97(H97), C19(H19), C43(H43), C163(H163), C101(H101),
 C157(H157), C70(H70), C190(H190), C98(H98), C209(H209), C100(H100), C220(H220),
  C42(H42), C162(H162), C129(H129), C184(H184), C185(H185), C72(H72),
 C141(H141), C108(H108), C126(H126), C80(H80), C182(H182), C51(H51), C169(H169),
  C183(H183), C113(H113), C181(H181), C136(H136), C22(H22), C216(H216),
 C153(H153), C85(H85), C76(H76), C79(H79), C132(H132), C219(H219), C210(H210),
 C228(H228), C21(H21), C54(H54), C212(H212), C213(H213), C52(H52), C156(H156),
 C1B(H1BA), C27(H27), C217(H217), C77(H77), C107(H107), C78(H78), C135(H135),
 C134(H134), C53(H53), C133(H133), C218(H218), C154(H154), C225(H225), C1D(H1D),
  C104(H104), C20(H20), C155(H155), C197(H197), C106(H106), C105(H105)
5.b X=CH2 refined with riding coordinates:
 C142(H14A,H14B), C86(H86A,H86B), C170(H17A,H17B), C114(H11A,H11B), C28(H28A,
 H28B), C198(H19J,H19K), C229(H22A,H22B)
5.c Idealised Me refined as rotating group:
 C82(H82A,H82B,H82C), C138(H13A,H13B,H13C), C83(H83A,H83B,H83C), C139(H13D,
 H13E,H13F), C222(H22C,H22D,H22E), C84(H84A,H84B,H84C), C223(H22F,H22G,H22H),
 C140(H14C,H14D,H14E), C24(H24A,H24B,H24C), C194(H19A,H19B,H19C), C195(H19D,
 H19E,H19F), C224(H22I,H22J,H22K), C196(H19G,H19H,H19I), C110(H11C,H11D,H11E),
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C166(H16A,H16B,H16C), C167(H16D,H16E,
 H16F), C111(H11F,H11G,H11H), C168(H16G,H16H,H16I), C233(H23J,H23K,H23L),
 C231(H23A,H23B,H23C), C230(H23D,H23E,H23F), C232(H23G,H23H,H23I), C2(H2A,H2B,
 H2C), C1(H1A,H1B,H1C), C3(H3A,H3B,H3C)
;
_shelx_res_checksum              71667
_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 1.359
_oxdiff_exptl_absorpt_empirical_full_min 0.823