Difunctionalization of C-C σ-Bonds Enabled by the Reaction of Bicyclo[1.1.0]butyl Boronate Complexes with Electrophiles: Reaction Development, Scope, and Stereochemical Origins.
Bennett, Steven H.; Fawcett, Alexander; Denton, Elliott H.; Biberger, Tobias; Fasano, Valerio; Winter, Nils; Aggarwal, Varinder K.; Journal of the American Chemical Society 142 (2020) 16766–16775; doi:10.1021/jacs.0c07357

data_4135254
_publ_section_title
;
 Difunctionalization of C-C \s-Bonds Enabled by the Reaction of
 Bicyclo[1.1.0]butyl Boronate Complexes with Electrophiles: Reaction
 Development, Scope, and Stereochemical Origins.
;
_journal_issue                   39
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              16766
_journal_page_last               16775
_journal_paper_doi               10.1021/jacs.0c07357
_journal_volume                  142
_journal_year                    2020
_chemical_formula_moiety         'C22 H33 B O4'
_chemical_formula_sum            'C22 H33 B O4'
_chemical_formula_weight         372.29
_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             2019-05-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.427(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.1029(5)
_cell_length_b                   11.3545(4)
_cell_length_c                   13.1218(5)
_cell_measurement_reflns_used    2757
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      24.25
_cell_measurement_theta_min      2.31
_cell_volume                     2078.53(13)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2016)'
_computing_data_collection       'Bruker Apex suite'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2016)'
_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      100(2)
_diffrn_detector                 'Bruker area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'Bruker Apex II kappa CCD area detector'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0440
_diffrn_reflns_av_unetI/netI     0.0396
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            16907
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         2.313
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.079
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6392
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0716 before and 0.0496 after correction. The Ratio of minimum to maximum transmission is 0.8573. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.190
_exptl_crystal_description       block
_exptl_crystal_F_000             808
_exptl_crystal_size_max          0.479
_exptl_crystal_size_mid          0.372
_exptl_crystal_size_min          0.304
_refine_diff_density_max         0.261
_refine_diff_density_min         -0.202
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     325
_refine_ls_number_reflns         4253
_refine_ls_number_restraints     265
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0719
_refine_ls_R_factor_gt           0.0499
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1460
_refine_ls_wR_factor_ref         0.1631
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3153
_reflns_number_total             4253
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c07357_si_005.cif
_cod_data_source_block           testm1
_cod_depositor_comments
'Adding full bibliography for 4135252--4135257.cif.'
_cod_database_code               4135254
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.976
_shelx_estimated_absorpt_t_min   0.963
_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, All O(H) groups
2. Restrained distances
 O1-C5 \\sim O1A-C5
 with sigma of 0.01
 O4-C18 \\sim O4A-C18A \\sim O3-C17 \\sim O3A-C17A
 with sigma of 0.01
 C18A-C17A \\sim C22-C18
 with sigma of 0.01
 O4A-B1 \\sim O4-B1 \\sim O3-B1 \\sim O3A-B1
 with sigma of 0.01
 C21A-C18A \\sim C22A-C18A \\sim C21-C18 \\sim C22-C18 \\sim C20A-C17A \\sim
C19A-C17A \\sim C20-C17 ~
 C19-C17
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O4 \\sim O3 \\sim C22 \\sim C20 \\sim C18 \\sim C21 \\sim C19 \\sim C17 \\sim
O4A \\sim C18A \\sim C17A \\sim O3A \\sim C22A \\sim C21A \\sim C19A \\sim
C20A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C21A) = Uanis(C19)
Uanis(C19A) = Uanis(C20)
4. Others
 Sof(H5B)=Sof(O1A)=Sof(H1AA)=1-FVAR(1)
 Sof(H5A)=Sof(O1)=Sof(H1A)=FVAR(1)
 Sof(O4A)=Sof(C18A)=Sof(C17A)=Sof(O3A)=Sof(C22A)=Sof(H22D)=Sof(H22E)=Sof(H22F)=
 Sof(C21A)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C19A)=Sof(H19D)=Sof(H19E)=
 Sof(H19F)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(2)
 Sof(O4)=Sof(O3)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C20)=Sof(H20A)=
 Sof(H20B)=Sof(H20C)=Sof(C18)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C19)=
 Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C17)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C1(H1), C12(H12), C5(H5A), C5(H5B)
5.b Secondary CH2 refined with riding coordinates:
 C4(H4B,H4A), C2(H2A,H2B), C13(H13A,H13B), C16(H16A,H16B), C14(H14A,H14B),
 C15(H15A,H15B)
5.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C7(H7), C10(H10), C8(H8), C9(H9)
5.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C19(H19A,H19B,
 H19C), C22A(H22D,H22E,H22F), C21A(H21D,H21E,H21F), C19A(H19D,H19E,H19F),
 C20A(H20D,H20E,H20F)
5.e Idealised tetrahedral OH refined as rotating group:
 O1(H1A), O1A(H1AA)
;
_shelx_res_checksum              40888
_shelx_hkl_checksum              42240
_olex2_submission_special_instructions 'No special instructions were received'