Total Synthesis of Isomalabaricane Triterpenoids.
Boyko, Yaroslav D.; Huck, Christopher J.; Sarlah, David; Journal of the American Chemical Society 141 (2019) 14131–14135; doi:10.1021/jacs.9b08487

data_4128797
_publ_section_title
;
 Total Synthesis of Isomalabaricane Triterpenoids.
;
_journal_issue                   36
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14131
_journal_page_last               14135
_journal_paper_doi               10.1021/jacs.9b08487
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C31 H54 O3 Si'
_chemical_formula_sum            'C31 H54 O3 Si'
_chemical_formula_weight         502.83
_chemical_name_systematic
'rel-(R)-1-((4aR,6S,8aS)-2,5,5,8a-tetramethyl-6-((triisopropylsilyl)oxy)-3,4,4a,5,6,7,8,8a-octahydronaphthalen-1-yl)prop-2-yn-1-yl pivalate'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-06-06 deposited with the CCDC.	2019-08-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.0050(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.2188(3)
_cell_length_b                   10.7692(4)
_cell_length_c                   39.2149(14)
_cell_measurement_reflns_used    23397
_cell_measurement_temperature    100
_cell_measurement_theta_max      25.36
_cell_measurement_theta_min      2.45
_cell_volume                     3044.4(2)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker Photon II area detector'
_diffrn_detector_type            'charge integrated pixel array'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'Mo Bruker D8 Venture/Photon II'
_diffrn_measurement_method       'profile data from \f and \w scans'
_diffrn_radiation_monochromator  'multilayer mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0804
_diffrn_reflns_av_unetI/netI     0.0377
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            68461
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.356
_diffrn_reflns_theta_min         2.158
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.105
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.4636
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1658 before and 0.0979 after correction. The Ratio of minimum to maximum transmission is 0.6221. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.097
_exptl_crystal_description       needle
_exptl_crystal_F_000             1112
_exptl_crystal_recrystallization_method 'Crystallized from acetonitrile'
_exptl_crystal_size_max          0.684
_exptl_crystal_size_mid          0.152
_exptl_crystal_size_min          0.116
_refine_diff_density_max         0.578
_refine_diff_density_min         -0.455
_refine_diff_density_rms         0.115
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.108
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     421
_refine_ls_number_reflns         5658
_refine_ls_number_restraints     117
_refine_ls_restrained_S_all      1.151
_refine_ls_R_factor_all          0.0688
_refine_ls_R_factor_gt           0.0607
_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^)+(0.0767P)^2^+4.7225P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1733
_refine_ls_wR_factor_ref         0.1823
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5058
_reflns_number_total             5658
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b08487_si_002.cif
_cod_data_source_block           dd81u_0m
_cod_database_code               4128797
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.988
_shelx_estimated_absorpt_t_min   0.932
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9610(7)
 0.0390(7)
2. 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, All C(H,H,H,H) groups
3. Restrained distances
 Si1-C26B \\sim Si1-C23A \\sim Si1-C23B \\sim Si1-C29A \\sim Si1-C29B \\sim
Si1-C26A
 with sigma of 0.01
 C24A-C23A \\sim C25A-C23A \\sim C23B-C24B \\sim C25B-C23B \\sim C29A-C31A
\\sim C30A-C29A \\sim C31B-
 C29B \\sim C30B-C29B \\sim C26A-C28A \\sim C27A-C26A \\sim C28B-C26B \\sim
C26B-C27B
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C27A \\sim C28B: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C28A \\sim C30B: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C30A \\sim C31B: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C25B \\sim C31A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C24A \\sim C24B: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C25A \\sim C27B: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
5. Others
 Sof(C23B)=Sof(H23B)=Sof(C24B)=Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C25B)=
 Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(C26B)=Sof(H26B)=Sof(C27B)=Sof(H27D)=
 Sof(H27E)=Sof(H27F)=Sof(C28B)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29B)=
 Sof(H29B)=Sof(C30B)=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C31B)=Sof(H31D)=
 Sof(H31E)=Sof(H31F)=1-FVAR(1)
 Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25A)=
 Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(H27A)=
 Sof(H27B)=Sof(H27C)=Sof(C28A)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29A)=
 Sof(H29A)=Sof(C30A)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C31A)=Sof(H31A)=
 Sof(H31B)=Sof(H31C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C3(H3), C5(H5), C11(H11), C23A(H23A), C23B(H23B), C26A(H26A), C26B(H26B),
 C29A(H29A), C29B(H29B)
6.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C6(H6A,H6B), C7(H7A,H7B)
6.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C),
 C24A(H24A,H24B,H24C), C24B(H24D,H24E,H24F), C25A(H25A,H25B,H25C), C25B(H25D,
 H25E,H25F), C27A(H27A,H27B,H27C), C27B(H27D,H27E,H27F), C28A(H28A,H28B,H28C),
 C28B(H28D,H28E,H28F), C30A(H30A,H30B,H30C), C30B(H30D,H30E,H30F), C31A(H31A,
 H31B,H31C), C31B(H31D,H31E,H31F)
;
_shelx_res_checksum              74638
_shelx_hkl_checksum              36933
_olex2_date_sample_data_collection 2019-04-10
_olex2_date_sample_submission    2019-04-09
_olex2_exptl_crystal_mounting_method
'Mounted on a Cryoloop (Hampton research) in Krytox oil with (1 -5 5)  face rougly perpendicular to the spindle axis'
_olex2_submission_original_sample_id dd81u
_olex2_submission_special_instructions 'No special instructions were received'