Total synthesis of (-)-scabrolide A and (-)-yonarolide.
Hafeman, Nicholas J.; Loskot, Steven A.; Reimann, Christopher E.; Pritchett, Beau P.; Virgil, Scott C.; Stoltz, Brian M.; Chemical science 14 (2023) 4745–4758; doi:10.1039/d3sc00651d

data_1568756
_publ_section_title
;
 Total synthesis of (-)-scabrolide A and (-)-yonarolide.
;
_journal_issue                   18
_journal_name_full               'Chemical science'
_journal_page_first              4745
_journal_page_last               4758
_journal_paper_doi               10.1039/d3sc00651d
_journal_volume                  14
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C16 H19 Cl O5, 0.5(H2 O), 0.09(C2 H2 Cl6)'
_chemical_formula_sum            'C16.19 H20.19 Cl1.59 O5.5'
_chemical_formula_weight         359.09
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2019-01-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
,
 SHELXL-2017/1, and manual edit
;
_audit_update_record
;
2023-02-05 deposited with the CCDC.	2023-03-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.960(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   34.102(5)
_cell_length_b                   14.485(2)
_cell_length_c                   6.6087(11)
_cell_measurement_reflns_used    9939
_cell_measurement_temperature    100
_cell_measurement_theta_max      74.72
_cell_measurement_theta_min      3.32
_cell_volume                     3252.3(9)
_computing_cell_refinement       'SAINT V8.38A (Bruker-AXS, 2016)'
_computing_data_collection
'BIS V6.2.9/2018-03-16 & APEX3 v2018.7-2 (Bruker-AXS, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker-AXS, 2016)'
_computing_molecular_graphics    'DIAMOND 3 (Crystal Impact, 1999)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT-2014/5 (Sheldrick, 2013)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'CPAD Area Detector'
_diffrn_detector_area_resol_mean 7.69
_diffrn_detector_type            'Bruker PHOTON II'
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.952
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'multilayer mirrors'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_unetI/netI     0.0792
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -41
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            6144
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.904
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         76.122
_diffrn_reflns_theta_min         3.317
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_current           1
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatec I\mS HB'
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.208
_exptl_absorpt_correction_T_max  0.9904
_exptl_absorpt_correction_T_min  0.7072
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;    
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. 
wR2(int) was 0.1382 before and 0.1055 after correction. 
The Ratio of minimum to maximum transmission is 0.7141. 
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.467
_exptl_crystal_description       blade
_exptl_crystal_F_000             1507
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.708
_refine_diff_density_min         -0.538
_refine_diff_density_rms         0.113
_refine_ls_abs_structure_details
;
 Flack x determined using 1819 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.163(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     434
_refine_ls_number_reflns         6144
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0969
_refine_ls_R_factor_gt           0.0840
_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^)+(0.0956P)^2^+21.9971P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2207
_refine_ls_wR_factor_ref         0.2291
_reflns_Friedel_coverage         0.824
_reflns_Friedel_fraction_full    0.952
_reflns_Friedel_fraction_max     0.852
_reflns_number_gt                5185
_reflns_number_total             6144
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc00651d2.cif
_cod_data_source_block           v18612
_cod_depositor_comments
'Adding full bibliography for 1568754--1568762.cif.'
_cod_original_cell_volume        3252.2(9)
_cod_original_formula_sum        'C16.19 H20.19 Cl1.59 O5.50'
_cod_database_code               1568756
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.910
_shelx_estimated_absorpt_t_min   0.719
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.846(7)
 0.154(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 O(H) groups, All O(H,H) groups
3. Restrained distances
 C17-Cl3 \\sim C17-Cl4 \\sim C17-Cl2
 with sigma of 0.02
4. Others
 Sof(Cl2)=Sof(Cl3)=Sof(Cl4)=Sof(C17)=Sof(H17)=FVAR(1)
5.a Everything fixed:
 H17
5.b Free rotating group:
 O6(H6E,H6F,Cl2,Cl3,Cl4,C17)
5.c Ternary CH refined with riding coordinates:
 C7(H7), C9(H9), C10(H10), C11(H11), C13(H13), C7B(H7B), C9B(H9B), C10B(H10B),
 C11B(H11B), C13B(H13B)
5.d Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C6(H6A,H6B), C14(H14A,H14B), C2B(H2C,
 H2D), C3B(H3C,H3D), C4B(H4D,H4C), C6B(H6C,H6D), C14B(H14C,H14D)
5.e Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C16B(H16D,H16E,H16F)
5.f Idealised tetrahedral OH refined as rotating group:
 O5(H5), O5B(H5B)
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_shelx_res_checksum              95214
_olex2_submission_special_instructions 'No special instructions were received'