Visible Light Excitation of BODIPYs Enables Dehydrogenative Enamination at Their α-Positions with Aliphatic Amines.
Wang, Dandan; Guo, Xing; Wu, Hao; Wu, Qinghua; Wang, Hua; Zhang, Xiankang; Hao, Erhong; Jiao, Lijuan; The Journal of organic chemistry 85 (2020) 8360–8370; doi:10.1021/acs.joc.0c00620

data_4038514
_publ_section_title
;
 Visible Light Excitation of BODIPYs Enables Dehydrogenative Enamination
 at Their \a-Positions with Aliphatic Amines.
;
_journal_issue                   13
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              8360
_journal_page_last               8370
_journal_paper_doi               10.1021/acs.joc.0c00620
_journal_volume                  85
_journal_year                    2020
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C30 H29 B Br2 Cl F2 N3'
_chemical_formula_sum            'C30 H29 B Br2 Cl F2 N3'
_chemical_formula_weight         675.64
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2019-12-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.7637(3)
_cell_length_b                   17.0551(7)
_cell_length_c                   20.6021(9)
_cell_measurement_reflns_used    9946
_cell_measurement_temperature    298.15
_cell_measurement_theta_max      27.26
_cell_measurement_theta_min      2.92
_cell_volume                     3079.3(2)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      298.15
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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  0.0571
_diffrn_reflns_av_unetI/netI     0.0207
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            134960
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.555
_diffrn_reflns_theta_min         2.794
_exptl_absorpt_coefficient_mu    2.755
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5675
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0875 before and 0.0566 after correction. The Ratio of minimum to maximum transmission is 0.7611. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.457
_exptl_crystal_description       block
_exptl_crystal_F_000             1360
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.017
_refine_diff_density_min         -0.632
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Flack x determined using 2005 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.4565(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     410
_refine_ls_number_reflns         7096
_refine_ls_number_restraints     86
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0815
_refine_ls_R_factor_gt           0.0574
_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^)+(0.0741P)^2^+4.5420P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1435
_refine_ls_wR_factor_ref         0.1622
_reflns_Friedel_coverage         0.783
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                5441
_reflns_number_total             7096
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00620_si_002.cif
_cod_data_source_block           mo_20191221c_0m
_cod_depositor_comments
'Adding full bibliography for 4038510--4038515.cif.'
_cod_database_code               4038514
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.609
_shelx_estimated_absorpt_t_min   0.595
_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
 C27-C28
 1.54 with sigma of 0.001
 C26-C25 \\sim C26A-C25
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C30A) \\sim Ueq, Uanis(C28A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C27, C28, C29, C30
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 N3, C25, C26, C27, C28, C29, C30
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 N3A, C25, C26A, C27A, C28A, C29A, C30A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Others
 Sof(N3A)=Sof(H25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(H27C)=Sof(H27D)=
 Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29A)=Sof(H29C)=Sof(H29D)=
 Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=1-FVAR(1)
 Sof(N3)=Sof(H25)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(C28)=
 Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(C30)=Sof(H30A)=
 Sof(H30B)=Sof(H30C)=FVAR(1)
6.a Riding coordinates:
 C28(H28A,H28B,H28C), C28A(H28D,H28E,H28F), C30(H30A,H30B,H30C), C30A(H30D,
 H30E,H30F)
6.b Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B), C27A(H27C,H27D), C29(H29A,H29B), C29A(H29C,H29D)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C11(H11), C12(H12), C14(H14), C15(H15), C18(H18), C20(H20),
 C25(H25), C25(H25A), C26(H26), C26A(H26A)
6.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              78401
_shelx_hkl_checksum              83414
_olex2_submission_special_instructions 'No special instructions were received'