Dimerizing Cascades of Enallenamides Reveal the Visible-Light- Promoted Activation of Cumulated C-C Double Bonds
Maestri, Giovanni; Serafino, Andrea; Chiminelli, Maurizio; Balestri, Davide; Marchiò, Luciano; Bigi, Franca; Maggi, Raimondo; Malacria, Max; Chemical Science  (2022) –; doi:10.1039/D1SC06719B

data_1566150
_publ_section_title
;
 Dimerizing Cascades of Enallenamides Reveal the Visible-Light- Promoted
 Activation of Cumulated C-C Double Bonds
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC06719B
_journal_year                    2022
_chemical_formula_moiety         'C48 H54 N2 O2'
_chemical_formula_sum            'C48 H54 N2 O2'
_chemical_formula_weight         690.93
_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             2021-11-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-11-08 deposited with the CCDC.	2022-01-25 downloaded from the CCDC.
;
_cell_angle_alpha                82.728(2)
_cell_angle_beta                 69.0860(10)
_cell_angle_gamma                80.532(2)
_cell_formula_units_Z            2
_cell_length_a                   10.9885(3)
_cell_length_b                   13.5620(3)
_cell_length_c                   14.3897(3)
_cell_measurement_reflns_used    9018
_cell_measurement_temperature    200
_cell_measurement_theta_max      69.547
_cell_measurement_theta_min      3.312
_cell_volume                     1970.50(8)
_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      200.0
_diffrn_detector_area_resol_mean 7.4
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker D8 Venture PhotonII'
_diffrn_measurement_method       'omega and theta scans'
_diffrn_radiation_monochromator  'multilayer mirror optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0460
_diffrn_reflns_av_unetI/netI     0.0219
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            75540
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.058
_diffrn_reflns_theta_min         3.297
_diffrn_source                   microfocus
_exptl_absorpt_coefficient_mu    0.538
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.6430
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0850 before and 0.0633 after correction. The Ratio of minimum to maximum transmission is 0.8536. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.164
_exptl_crystal_description       block
_exptl_crystal_F_000             744
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.890
_refine_diff_density_min         -0.391
_refine_diff_density_rms         0.049
_refine_ls_extinction_coef       0.0022(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     487
_refine_ls_number_reflns         7479
_refine_ls_number_restraints     62
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0846
_refine_ls_R_factor_gt           0.0688
_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^)+(0.1097P)^2^+0.9281P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1912
_refine_ls_wR_factor_ref         0.2119
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5861
_reflns_number_total             7479
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc06719b2.cif
_cod_data_source_block           cu_as620mae_0m
_cod_original_cell_volume        1970.51(8)
_cod_database_code               1566150
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.963
_shelx_estimated_absorpt_t_min   0.953
_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
 C45A-C44A = C45-C44
 1.5 with sigma of 0.02
 C45-C44 = C45A-C44 = C46A-C45A = C46-C45 = C47-C46 = C47A-C46A
 1.5 with sigma of 0.02
 C44A-C41 = C44-C41
 1.48 with sigma of 0.02
 C44-C46
 2.55 with sigma of 0.04
 C45-C47
 2.55 with sigma of 0.04
 C44A-C46A
 2.55 with sigma of 0.04
 C45A-C47A
 2.55 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C33 \\sim C34 \\sim C36 \\sim C37: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02
C40 \\sim C42 \\sim C43 \\sim C41 \\sim C39 \\sim C38: within 1.7A with sigma
of 0.01 and sigma for terminal atoms of 0.01
Uanis(C40) = Uanis(C41) = Uanis(C42)
4. Others
 Sof(C45A)=Sof(H45C)=Sof(H45D)=Sof(C46A)=Sof(H46C)=Sof(H46D)=Sof(C47A)=
 Sof(H47D)=Sof(H47E)=Sof(H47F)=Sof(C44A)=Sof(H44C)=Sof(H44D)=1-FVAR(1)
 Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(C46)=Sof(H46A)=
 Sof(H46B)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C5(H5), C7(H7), C3(H3)
5.b Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C11(H11A,H11B), C31(H31A,H31B), C20(H20A,H20B), C21(H21A,
 H21B), C44(H44A,H44B), C22(H22A,H22B), C45(H45A,H45B), C46(H46A,H46B),
 C45A(H45C,H45D), C46A(H46C,H46D), C44A(H44C,H44D)
5.c Me refined with riding coordinates:
 C47A(H47D,H47E,H47F)
5.d Aromatic/amide H refined with riding coordinates:
 C9(H9), C30(H30), C33(H33), C34(H34), C35(H35), C36(H36), C37(H37), C26(H26),
 C15(H15), C39(H39), C43(H43), C19(H19), C40(H40), C29(H29), C18(H18), C16(H16),
  C27(H27), C42(H42), C28(H28)
5.e Fitted hexagon refined as free rotating group:
 C32(C33,C34,C35,C36,C37)
5.f X=CH2 refined with riding coordinates:
 C12(H12A,H12B)
5.g Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C48(H48A,H48B,H48C), C23(H23A,H23B,H23C), C47(H47A,H47B,
 H47C)
;