Stereoselective synthesis of an advanced <i>trans</i>-decalin intermediate towards the total synthesis of anthracimycin.
Jeanmard, Laksamee; Lodovici, Giacomo; George, Ian; Bray, Joshua T. W.; Whitwood, Adrian C.; Thomas, Gavin H.; Fairlamb, Ian J. S.; Unsworth, William P.; Clarke, Paul A.; Chemical communications (Cambridge, England) 60 (2024) 5699–5702; doi:10.1039/d4cc01738b

data_7133012
_publ_section_title
;
 Stereoselective synthesis of an advanced <i>trans</i>-decalin
 intermediate towards the total synthesis of anthracimycin.
;
_journal_issue                   44
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              5699
_journal_page_last               5702
_journal_paper_doi               10.1039/d4cc01738b
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C26.999 H41.998 N4 O5 Si'
_chemical_formula_sum            'C27 H42 N4 O5 Si'
_chemical_formula_weight         530.73
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-20
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-03-20 deposited with the CCDC.	2024-05-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.909(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.8380(6)
_cell_length_b                   15.1690(5)
_cell_length_c                   15.0877(5)
_cell_measurement_reflns_used    3413
_cell_measurement_temperature    110.00(14)
_cell_measurement_theta_max      70.9800
_cell_measurement_theta_min      4.5580
_cell_volume                     2863.91(19)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_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 (Sheldrick, 2015)'
_diffrn_ambient_temperature      110.00(14)
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     48.00 109.00   1.00   80.00    --   54.00  57.00 -30.00   61
  2  \w     84.00 178.00   1.00   90.00    --  108.00  25.00 -60.00   94
  3  \w     59.00 104.00   1.00   90.00    --  108.00 -50.00 150.00   45
  4  \w     46.00 110.00   1.00   90.00    --  108.00-111.00 120.00   64
  5  \w     38.00  92.00   1.00   90.00    --  108.00 -37.00  30.00   54
  6  \w     48.00  92.00   1.00   90.00    --  108.00 -25.00 -30.00   44
  7  \w     38.00  92.00   1.00   90.00    --  108.00 -37.00 -60.00   54
  8  \w     36.00  79.00   1.00   80.00    --   54.00 -77.00 -90.00   43
  9  \w    -15.00  17.00   1.00   80.00    --   54.00 -77.00 -90.00   32
 10  \w    -15.00  24.00   1.00   20.00    --    0.00  57.00 120.00   39
 11  \w     37.00  78.00   1.00   90.00    --  108.00 -37.00 120.00   41
 12  \w     27.00  73.00   1.00   80.00    --   54.00 -57.00 120.00   46
 13  \w     27.00  68.00   1.00   20.00    --    0.00  57.00 120.00   41
 14  \w     25.00 118.00   1.00   80.00    --   54.00  77.00  30.00   93
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0230
_diffrn_reflns_av_unetI/netI     0.0403
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            8867
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.070
_diffrn_reflns_theta_max         67.070
_diffrn_reflns_theta_min         4.187
_exptl_absorpt_coefficient_mu    1.067
_exptl_absorpt_correction_T_max  0.997
_exptl_absorpt_correction_T_min  0.972
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.231
_exptl_crystal_description       needle
_exptl_crystal_F_000             1144
_exptl_crystal_size_max          0.213
_exptl_crystal_size_mid          0.043
_exptl_crystal_size_min          0.015
_refine_diff_density_max         0.319
_refine_diff_density_min         -0.273
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     409
_refine_ls_number_reflns         5044
_refine_ls_number_restraints     82
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0606
_refine_ls_R_factor_gt           0.0472
_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^)+(0.0429P)^2^+1.5214P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1100
_refine_ls_wR_factor_ref         0.1172
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4168
_reflns_number_total             5044
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc01738b2.cif
_cod_data_source_block           pac1612
_cod_depositor_comments
'Adding full bibliography for 7133012--7133013.cif.'
_cod_original_cell_volume        2863.93(19)
_cod_database_code               7133012
_shelx_shelxl_version_number     2018/3
_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
 C27B-C25B = C27A-C25A = C27C-C25C = C26C-C25C = C26A-C25A = C26B-C25B
 1.524 with sigma of 0.001
 C27A-C26A = C27C-C26C = C27B-C26B
 2.46 with sigma of 0.01
 C20-C19 \\sim C21-C19 \\sim C19-C20A \\sim C19-C21A
 with sigma of 0.005
 C23-C22 \\sim C23A-C22A \\sim C24-C22 \\sim C24A-C22A
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(C27C) \\sim Ueq, Uanis(C27A) \\sim Ueq, Uanis(C27B) \\sim Ueq,
Uanis(C26B) \\sim Ueq, Uanis(C26C) \\sim Ueq, Uanis(C26A) \\sim Ueq, Uanis(C20)
\\sim Ueq, Uanis(C20A) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C21A) \\sim Ueq:
with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C24) = Uanis(C24A)
Uanis(C23) = Uanis(C23A)
Uanis(C26B) = Uanis(C26A)
Uanis(C27A) = Uanis(C27C)
Uanis(C25B) = Uanis(C25A)
Uanis(C25A) = Uanis(C25B) = Uanis(C25C)
Uanis(C22) = Uanis(C22A)
Uanis(C21) = Uanis(C21A)
4. Others
 1*[Sof(C25B)+Sof(H25B)+Sof(C26B)+Sof(H26D)+Sof(H26E)+Sof(H26F)+Sof(C27B)+
 Sof(H27D)+Sof(H27E)+Sof(H27F)]+1*[Sof(C25A)+Sof(H25A)+Sof(C26A)+Sof(H26A)+
 Sof(H26B)+Sof(H26C)+Sof(C27A)+Sof(H27A)+Sof(H27B)+Sof(H27C)]+1*[Sof(C25C)+
 Sof(H25C)+Sof(C26C)+Sof(H26G)+Sof(H26H)+Sof(H26I)+Sof(C27C)+Sof(H27G)+
 Sof(H27H)+Sof(H27I)]=1 with esd of 0.001
 Sof(H19A)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C21A)=Sof(H21D)=
 Sof(H21E)=Sof(H21F)=1-FVAR(1)
 Sof(H19)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C21)=Sof(H21A)=Sof(H21B)=
 Sof(H21C)=FVAR(1)
 Sof(C22A)=Sof(H22A)=Sof(C23A)=Sof(H23D)=Sof(H23E)=Sof(H23F)=Sof(C24A)=
 Sof(H24D)=Sof(H24E)=Sof(H24F)=1-FVAR(2)
 Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C24)=Sof(H24A)=
 Sof(H24B)=Sof(H24C)=FVAR(2)
 Sof(C25B)=Sof(H25B)=Sof(C26B)=Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(C27B)=
 Sof(H27D)=Sof(H27E)=Sof(H27F)=FVAR(3)
 Sof(C25A)=Sof(H25A)=Sof(C26A)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C27A)=
 Sof(H27A)=Sof(H27B)=Sof(H27C)=FVAR(4)
 Sof(C25C)=Sof(H25C)=Sof(C26C)=Sof(H26G)=Sof(H26H)=Sof(H26I)=Sof(C27C)=
 Sof(H27G)=Sof(H27H)=Sof(H27I)=FVAR(5)
5.a Ternary CH refined with riding coordinates:
 C2(H2), C6(H6), C7(H7), C19(H19), C19(H19A), C22(H22), C22A(H22A), C25A(H25A),
  C25B(H25B), C25C(H25C)
5.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B), C4(H4A,H4B), C8(H8A,H8B), C11(H11A,H11B)
5.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C15(H15), C17(H17), C18(H18)
5.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C20(H20A,H20B,H20C), C20A(H20D,H20E,H20F), C21(H21A,H21B,
 H21C), C21A(H21D,H21E,H21F), C23(H23A,H23B,H23C), C23A(H23D,H23E,H23F),
 C24(H24A,H24B,H24C), C24A(H24D,H24E,H24F), C26A(H26A,H26B,H26C), C26B(H26D,
 H26E,H26F), C26C(H26G,H26H,H26I), C27A(H27A,H27B,H27C), C27B(H27D,H27E,H27F),
 C27C(H27G,H27H,H27I)
;
_shelx_res_checksum              65501
_shelx_hkl_checksum              39587
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;