Ring-Expansion Induced 1,2-Metalate Rearrangements: Highly Diastereoselective Synthesis of Cyclobutyl Boronic Esters.
Hari, Durga Prasad; Abell, Joseph C.; Fasano, Valerio; Aggarwal, Varinder K.; Journal of the American Chemical Society 142 (2020) 5515–5520; doi:10.1021/jacs.0c00813

data_4134396
_publ_section_title
;
 Ring-Expansion Induced 1,2-Metalate Rearrangements: Highly
 Diastereoselective Synthesis of Cyclobutyl Boronic Esters.
;
_journal_issue                   12
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5515
_journal_page_last               5520
_journal_paper_doi               10.1021/jacs.0c00813
_journal_volume                  142
_journal_year                    2020
_chemical_formula_moiety         '0.743(Cl), C20 H33 B N O2, 0.257(I)'
_chemical_formula_sum            'C20 H33 B Cl0.74 I0.26 N O2'
_chemical_formula_weight         389.28
_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             2020-02-19
_audit_creation_method
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.2370(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.8872(12)
_cell_length_b                   9.0985(6)
_cell_length_c                   14.5635(10)
_cell_measurement_reflns_used    4339
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.48
_cell_measurement_theta_min      2.47
_cell_volume                     2186.8(3)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'Bruker Apex II kappa CCD area detector'
_diffrn_measurement_device_type  'Bruker Apex II kappa CCD area detector'
_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  0.0430
_diffrn_reflns_av_unetI/netI     0.0402
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            19323
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.909
_diffrn_reflns_theta_min         2.468
_diffrn_source                   'fine-focus sealed tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.35
_diffrn_source_voltage           45.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.519
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6242
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0672 before and 0.0462 after correction.
The Ratio of minimum to maximum transmission is 0.8372.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.182
_exptl_crystal_description       plate
_exptl_crystal_F_000             829
_exptl_crystal_size_max          0.415
_exptl_crystal_size_mid          0.342
_exptl_crystal_size_min          0.184
_refine_diff_density_max         0.397
_refine_diff_density_min         -0.227
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     274
_refine_ls_number_reflns         5226
_refine_ls_number_restraints     152
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.0556
_refine_ls_R_factor_gt           0.0366
_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^)+(0.0397P)^2^+0.4843P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0828
_refine_ls_wR_factor_ref         0.0902
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4021
_reflns_number_total             5226
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c00813_si_002.cif
_cod_data_source_block           dp_41
_cod_depositor_comments
'Adding full bibliography for 4134395--4134396.cif.'
_cod_database_code               4134396
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.911
_shelx_estimated_absorpt_t_min   0.814
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C18-C17 \\sim C18A-C17
 with sigma of 0.01
 N1-C18 \\sim N1A-C18A
 with sigma of 0.01
 N1-C20 \\sim N1A-C20A \\sim N1-C19 \\sim N1A-C19A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C18 \\sim C18A \\sim N1 \\sim N1A \\sim C19 \\sim C19A \\sim C20 \\sim C20A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(N1) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C20)
\\sim Ueq, Uanis(C18A) \\sim Ueq, Uanis(N1A) \\sim Ueq, Uanis(C20A) \\sim Ueq,
Uanis(C19A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(I1A) = Uanis(Cl1)
4. Others
 Sof(H17C)=Sof(H17D)=Sof(C18A)=Sof(H18C)=Sof(H18D)=Sof(N1A)=Sof(H1AA)=
 Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C19A)=Sof(H19D)=Sof(H19E)=
 Sof(H19F)=Sof(I1A)=1-FVAR(1)
 Sof(Cl1)=Sof(N1)=Sof(H1)=Sof(H17A)=Sof(H17B)=Sof(C18)=Sof(H18A)=Sof(H18B)=
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=
 FVAR(1)
5.a Ternary CH refined with riding coordinates:
 N1(H1), C4(H4), N1A(H1AA)
5.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C17(H17A,H17B), C17(H17C,H17D), C1(H1A,H1B), C18(H18A,H18B),
 C18A(H18C,H18D)
5.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C6(H6), C7(H7), C9(H9), C8(H8)
5.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C14(H14A,H14B,H14C), C13(H13A,H13B,
 H13C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C20A(H20D,H20E,H20F),
 C19A(H19D,H19E,H19F)
;
_shelx_res_checksum              27929
_shelx_hkl_checksum              86728
_olex2_submission_special_instructions 'No special instructions were received'