Palladium-catalyzed distal γ- and ε-benzylation, allylation and allenylation of enones.
Sah, Pooja; Kapur, Manmohan; Chemical communications (Cambridge, England) 61 (2025) 1874–1877; doi:10.1039/d4cc05607h

data_7134106
_publ_section_title
;
 Palladium-catalyzed distal &#x3b3;- and &#x3b5;-benzylation, allylation
 and allenylation of enones.
;
_journal_issue                   9
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              1874
_journal_page_last               1877
_journal_paper_doi               10.1039/d4cc05607h
_journal_volume                  61
_journal_year                    2025
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C15 H17 N O3'
_chemical_formula_sum            'C15 H17 N O3'
_chemical_formula_weight         259.29
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-02-26
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-03-26 deposited with the CCDC.	2024-12-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.1533(11)
_cell_length_b                   12.457(3)
_cell_length_c                   14.899(2)
_cell_measurement_reflns_used    1364
_cell_measurement_temperature    99.00
_cell_measurement_theta_max      33.550
_cell_measurement_theta_min      2.131
_cell_volume                     1327.6(4)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      99.00
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.929
_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  0.0818
_diffrn_reflns_av_unetI/netI     0.1163
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.929
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            10550
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.892
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.550
_diffrn_reflns_theta_min         2.131
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.090
_exptl_absorpt_correction_T_max  0.7466
_exptl_absorpt_correction_T_min  0.4869
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1188 before and 0.0731 after correction.
The Ratio of minimum to maximum transmission is 0.6522.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear yellowish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.297
_exptl_crystal_description       block
_exptl_crystal_F_000             552
_exptl_crystal_size_max          0.153
_exptl_crystal_size_mid          0.136
_exptl_crystal_size_min          0.124
_refine_diff_density_max         0.323
_refine_diff_density_min         -0.240
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 711 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   1.2(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     202
_refine_ls_number_reflns         4670
_refine_ls_number_restraints     194
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.1317
_refine_ls_R_factor_gt           0.0753
_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^)+(0.0874P)^2^+0.0339P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1722
_refine_ls_wR_factor_ref         0.2105
_reflns_Friedel_coverage         0.693
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.843
_reflns_number_gt                2663
_reflns_number_total             4670
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc05607h2.cif
_cod_data_source_block           PO_04_89
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_atom_sites_solution_primary' value 'DUAL' was changed to
'dual' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 7134105--7134106.cif.
;
_cod_database_code               7134106
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.989
_shelx_estimated_absorpt_t_min   0.986
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C14-C13 \\sim C14A-C13A
 with sigma of 0.02
 C15-C13 \\sim C15A-C13A
 with sigma of 0.02
 C14-C15 \\sim C14A-C15A
 with sigma of 0.04
 C9-C14 \\sim C9-C14A
 with sigma of 0.02
 C12-C13 \\sim C12-C13A
 with sigma of 0.02
 C12-C15 \\sim C12-C15A
 with sigma of 0.04
 C9-C13 \\sim C9-C13A
 with sigma of 0.04
 C14-C12 \\sim C14A-C12
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
O3 \\sim C2 \\sim C4 \\sim C14A \\sim C3 \\sim C14 \\sim N1 \\sim C15 \\sim C8
\\sim C13 \\sim O2 \\sim C12 \\sim C6 \\sim C13A \\sim C7 \\sim C15A \\sim C1
\\sim C10 \\sim C11 \\sim C5 \\sim O1 \\sim C9: within 2A with sigma of 0.002
and sigma for terminal atoms of 0.004 within 2A
C6 \\sim C3 \\sim N1 \\sim O1 \\sim C2 \\sim C1 \\sim C8 \\sim O2 \\sim C7
\\sim C5 \\sim C4: within 2A with sigma of 0.002 and sigma for terminal atoms
of 0.004 within 2A
C6 \\sim C1 \\sim C2 \\sim C7 \\sim C3 \\sim N1 \\sim C5 \\sim O1 \\sim O2
\\sim C4 \\sim C8: within 2A with sigma of 0.002 and sigma for terminal atoms
of 0.004 within 2A
4. Others
 Sof(H12C)=Sof(H12D)=Sof(C14A)=Sof(H14C)=Sof(H14D)=Sof(C13A)=Sof(H13A)=
 Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=1-FVAR(1)
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H12A)=Sof(H12B)=Sof(C15)=Sof(H15A)=Sof(H15B)=
 Sof(H15C)=Sof(C13)=Sof(H13)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C13(H13), C13A(H13A)
5.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C7(H7A,H7B), C14(H14A,H14B), C12(H12A,H12B), C12(H12C,H12D),
 C14A(H14C,H14D)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C6(H6), C2(H2), C10(H10)
5.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C15A(H15D,H15E,H15F)
;
_shelx_res_checksum              78195
_shelx_hkl_checksum              29294
_olex2_submission_original_sample_id PO_04_89
_olex2_submission_special_instructions 'No special instructions were received'