Eco-friendly α,β-C(sp<sup>3</sup>)-H difunctionalization of tertiary amines <i>via</i> sequential [1,5]-hydride transfer and hetero-Diels-Alder cyclization.
Zhang, Yi; Yan, Huihui; Zhao, Peng; Chen, Rener; Fang, Weiwei; Wang, Lei; Ma, Yongmin; Chemical communications (Cambridge, England) 60 (2024) 10712–10715; doi:10.1039/d4cc02858a

data_7133631
_publ_section_title
;
 Eco-friendly &#x3b1;,&#x3b2;-C(sp<sup>3</sup>)-H difunctionalization of
 tertiary amines <i>via</i> sequential [1,5]-hydride transfer and
 hetero-Diels-Alder cyclization.
;
_journal_issue                   77
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              10712
_journal_page_last               10715
_journal_paper_doi               10.1039/d4cc02858a
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C39 H45 N3 O2'
_chemical_formula_sum            'C39 H45 N3 O2'
_chemical_formula_weight         587.78
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-08-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-08-05 deposited with the CCDC.	2024-08-28 downloaded from the CCDC.
;
_cell_angle_alpha                105.788(2)
_cell_angle_beta                 92.153(2)
_cell_angle_gamma                109.699(2)
_cell_formula_units_Z            2
_cell_length_a                   9.5701(5)
_cell_length_b                   12.7196(8)
_cell_length_c                   14.9523(9)
_cell_measurement_reflns_used    4873
_cell_measurement_temperature    273(2)
_cell_measurement_theta_max      27.87
_cell_measurement_theta_min      2.60
_cell_volume                     1632.07(17)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 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      273.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.995
_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  0.0711
_diffrn_reflns_av_unetI/netI     0.0512
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            35820
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.302
_diffrn_reflns_theta_min         2.284
_exptl_absorpt_coefficient_mu    0.074
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.7180
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0974 before and 0.0657 after correction.
The Ratio of minimum to maximum transmission is 0.9629.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.196
_exptl_crystal_description       block
_exptl_crystal_F_000             632
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.266
_refine_diff_density_min         -0.250
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     398
_refine_ls_number_reflns         8087
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0943
_refine_ls_R_factor_gt           0.0547
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0667P)^2^+0.3316P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1314
_refine_ls_wR_factor_ref         0.1655
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4896
_reflns_number_total             8087
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc02858a2.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 7133630--7133631.cif.'
_cod_database_code               7133631
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.983
_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.a Ternary CH refined with riding coordinates:
 C12(H12), C25(H25), C24(H24)
2.b Secondary CH2 refined with riding coordinates:
 C28(H28A,H28B), C26(H26A,H26B), C27(H27A,H27B), C35(H35A,H35B), C19(H19A,
 H19B), C39(H39A,H39B), C36(H36A,H36B), C22(H22A,H22B), C20(H20A,H20B),
 C21(H21A,H21B), C23(H23A,H23B), C38(H38A,H38B), C37(H37A,H37B)
2.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C10(H10), C1(H1), C17(H17), C16(H16), C15(H15), C4(H4), C30(H30),
 C2(H2), C3(H3), C33(H33), C31(H31), C32(H32)
2.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C)
;
_shelx_res_checksum              31361
_shelx_hkl_checksum              67059
_olex2_submission_special_instructions 'No special instructions were received'