Synthesis of gem-di(boryl)cyclopropanes from non-activated olefins via Mn-photocatalyzed atom transfer radical addition
Hu, Jiefeng; Zhang, Kun; Wang, Jing; Huang, Mingming; Chen, Shuangru; Shi, Zhuangzhi; Marder, Todd B.; Chemical Science 16 (2025) 10595–10601; doi:10.1039/D5SC02670A

data_1574598
_publ_section_title
;
 Synthesis of gem-di(boryl)cyclopropanes from non-activated olefins via
 Mn-photocatalyzed atom transfer radical addition
;
_journal_issue                   23
_journal_name_full               'Chemical Science'
_journal_page_first              10595
_journal_page_last               10601
_journal_paper_doi               10.1039/D5SC02670A
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C22 H34 B2 O4'
_chemical_formula_sum            'C22 H34 B2 O4'
_chemical_formula_weight         384.11
_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             2024-09-06
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6403)
;
_audit_update_record
;
2024-09-07 deposited with the CCDC.	2025-05-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 115.425(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.1753(17)
_cell_length_b                   15.5076(19)
_cell_length_c                   12.1845(15)
_cell_measurement_reflns_used    3670
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      19.96
_cell_measurement_theta_min      2.63
_cell_volume                     2248.4(5)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1187
_diffrn_reflns_av_unetI/netI     0.1008
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            27543
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.280
_diffrn_reflns_theta_min         2.269
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.074
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.4992
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0914 before and 0.0779 after correction.
The Ratio of minimum to maximum transmission is 0.6699.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear whiteish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.135
_exptl_crystal_description       block
_exptl_crystal_F_000             832
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.403
_refine_diff_density_min         -0.504
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     302
_refine_ls_number_reflns         4056
_refine_ls_number_restraints     132
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.2089
_refine_ls_R_factor_gt           0.0988
_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^)+(0.1205P)^2^+2.2785P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2314
_refine_ls_wR_factor_ref         0.2878
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1855
_reflns_number_total             4056
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02670a2.cif
_cod_data_source_block           1_a
_cod_depositor_comments          'Adding full bibliography for 1574598.cif.'
_cod_database_code               1574598
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.994
_shelx_estimated_absorpt_t_min   0.991
_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
 C21A-C20 = C21-C20 = C22A-C20 = C22-C20 = C20-C17 = C18-C17 = C18A-C17 = C19A-
 C17 = C19-C17
 1.54 with sigma of 0.01
 C18-C19 \\sim C18A-C19A \\sim C21-C22 \\sim C21A-C22A
 with sigma of 0.01
3. Rigid bond restraints
 C17, C18, C19, C20, C21, C22, C22A, C21A, C18A, C19A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C22A \\sim C21A
\\sim C19A \\sim C18A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
5. Others
 Sof(C22A)=Sof(H22D)=Sof(H22E)=Sof(H22F)=Sof(C21A)=Sof(H21D)=Sof(H21E)=
 Sof(H21F)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C19A)=Sof(H19D)=
 Sof(H19E)=Sof(H19F)=1-FVAR(1)
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=
 FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C9(H9)
6.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C10(H10A,H10B)
6.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16)
6.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C18(H18A,
 H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C),
 C22A(H22D,H22E,H22F), C21A(H21D,H21E,H21F), C18A(H18D,H18E,H18F), C19A(H19D,
 H19E,H19F)
;
_shelx_res_checksum              40074
_olex2_submission_special_instructions 'No special instructions were received'