Total Synthesis of Dapholdhamine B and Dapholdhamine B Lactone.
Guo, Lian-Dong; Hou, Jieping; Tu, Wentong; Zhang, Yan; Zhang, Yue; Chen, Louxi; Xu, Jing; Journal of the American Chemical Society 141 (2019) 11713–11720; doi:10.1021/jacs.9b05641

data_4127389
_publ_section_title
;
 Total Synthesis of Dapholdhamine B and Dapholdhamine B Lactone.
;
_journal_issue                   29
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11713
_journal_page_last               11720
_journal_paper_doi               10.1021/jacs.9b05641
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C36 H41 N O7 S'
_chemical_formula_sum            'C36 H41 N O7 S'
_chemical_formula_weight         631.76
_space_group_crystal_system      hexagonal
_space_group_IT_number           171
_space_group_name_Hall           'P 62'
_space_group_name_H-M_alt        'P 62'
_symmetry_space_group_name_Hall  'P 62'
_symmetry_space_group_name_H-M   'P 62'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-09-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            24
_cell_length_a                   38.5549(16)
_cell_length_b                   38.5549(16)
_cell_length_c                   14.8445(7)
_cell_measurement_reflns_used    9978
_cell_measurement_temperature    100
_cell_measurement_theta_max      25.76
_cell_measurement_theta_min      2.44
_cell_volume                     19109.8(14)
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker PHOTO 100 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker PHOTO 100 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1033
_diffrn_reflns_av_unetI/netI     0.0565
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       50
_diffrn_reflns_limit_h_min       -50
_diffrn_reflns_limit_k_max       50
_diffrn_reflns_limit_k_min       -50
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            376855
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.564
_diffrn_reflns_theta_min         2.113
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.155
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.7070
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1072 before and 0.0707 after correction. The Ratio of minimum to maximum transmission is 0.9482. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.318
_exptl_crystal_description       block
_exptl_crystal_F_000             8064
_exptl_crystal_size_max          0.41
_exptl_crystal_size_mid          0.38
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.371
_refine_diff_density_min         -0.334
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
'Flack x determined using 16110 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).'
_refine_ls_abs_structure_Flack   0.019(15)
_refine_ls_extinction_coef       0.00023(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.121
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1664
_refine_ls_number_reflns         29386
_refine_ls_number_restraints     74
_refine_ls_restrained_S_all      1.121
_refine_ls_R_factor_all          0.0787
_refine_ls_R_factor_gt           0.0542
_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^)+(0.0353P)^2^+6.6214P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0952
_refine_ls_wR_factor_ref         0.1020
_reflns_Friedel_coverage         0.924
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                23768
_reflns_number_total             29386
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b05641_si_002.cif
_cod_data_source_block           cxy0484_0m_pl
_cod_original_cell_volume        19109.8(18)
_cod_database_code               4127389
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.964
_shelx_estimated_absorpt_t_min   0.939
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 O22, C1A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C6 \\sim O3 \\sim C5 \\sim C7 \\sim C8 \\sim C2 \\sim C3 \\sim C4: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
C1A \\sim O22 \\sim C104: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C1A) \\sim Ueq, Uanis(C105) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C13) = Uanis(C6)
Uanis(O3) = Uanis(O4)
Uanis(C12) = Uanis(C5)
Uanis(C11) = Uanis(C7)
Uanis(C10) = Uanis(C8)
Uanis(C9) = Uanis(C2)
Uanis(C151) = Uanis(C3)
Uanis(C14) = Uanis(C4)
Uanis(C1A) = Uanis(C105)
4. Others
 Sof(O4)=Sof(H1BC)=Sof(H1BD)=Sof(C9)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=
 Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)=Sof(C12)=Sof(C14)=Sof(H14)=Sof(C151)=
 Sof(H151)=Sof(C1A)=Sof(H1AC)=Sof(H1AD)=Sof(H1AE)=1-FVAR(1)
 Sof(O3)=Sof(H1AA)=Sof(H1AB)=Sof(C2)=Sof(C5)=Sof(C6)=Sof(H6A)=Sof(H6B)=
 Sof(H6C)=Sof(C7)=Sof(H7)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=Sof(C8)=Sof(H8)=
 Sof(C105)=Sof(H10C)=Sof(H10D)=Sof(H10E)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C16(H16), C20(H20), C21(H21), C44(H44), C48(H48), C49(H49), C80(H80),
 C84(H84), C85(H85), C116(H116), C120(H120), C121(H121)
5.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C18(H18A,H18B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,
 H26B), C27(H27A,H27B), C28(H28A,H28B), C1(H1AA,H1AB), C1(H1BC,H1BD), C43(H43A,
 H43B), C46(H46A,H46B), C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B),
 C55(H55A,H55B), C56(H56A,H56B), C64(H64A,H64B), C79(H79A,H79B), C82(H82A,H82B),
  C88(H88A,H88B), C89(H89A,H89B), C90(H90A,H90B), C91(H91A,H91B), C92(H92A,
 H92B), C100(H10A,H10B), C115(H11D,H11E), C118(H11F,H11G), C124(H12A,H12B),
 C125(H12C,H12D), C126(H12E,H12F), C127(H12G,H12H), C128(H12I,H12J), C136(H13G,
 H13H)
5.c Aromatic/amide H refined with riding coordinates:
 C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C7(H7), C37(H37), C38(H38),
 C40(H40), C41(H41), C3(H3), C4(H4), C8(H8), C10(H10), C11(H11), C14(H14),
 C58(H58), C59(H59), C60(H60), C61(H61), C62(H62), C66(H66), C67(H67), C70(H70),
  C71(H71), C73(H73), C74(H74), C76(H76), C77(H77), C94(H94), C95(H95),
 C96(H96), C97(H97), C98(H98), C102(H102), C103(H103), C106(H106), C107(H107),
 C109(H109), C110(H110), C112(H112), C113(H113), C130(H130), C131(H131),
 C132(H132), C133(H133), C134(H134), C138(H138), C139(H139), C142(H142),
 C143(H143), C145(H145), C146(H146), C148(H148), C149(H149), C151(H151)
5.d Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C6(H6A,H6B,H6C), C42(H42A,H42B,H42C), C13(H13A,H13B,
 H13C), C63(H63A,H63B,H63C), C69(H69A,H69B,H69C), C78(H78A,H78B,H78C), C99(H99A,
 H99B,H99C), C105(H10C,H10D,H10E), C114(H11A,H11B,H11C), C135(H13D,H13E,H13F),
 C141(H14A,H14B,H14C), C150(H15C,H15D,H15E), C1A(H1AC,H1AD,H1AE)
;
_olex2_submission_special_instructions 'No special instructions were received'