Asymmetric Total Synthesis of Fusarentin 6-Methyl Ether and Its Biomimetic Transformation into Fusarentin 6,7-Dimethyl Ether, 7-O-Demethylmonocerin, and (+)-Monocerin
Bowen Fang; Xingang Xie; Changgui Zhao; Peng Jing; Huilin Li; Zhengshen Wang; Jixiang Gu; Xuegong She; Journal of Organic Chemistry 78 (2013) 6338–6343; doi:10.1021/jo400760q

data_4028350
_publ_contact_author_name
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;
_publ_section_title
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 Asymmetric Total Synthesis of Fusarentin 6-Methyl Ether and Its
 Biomimetic Transformation into Fusarentin 6,7-Dimethyl Ether,
 7-O-Demethylmonocerin, and (+)-Monocerin
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_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              6338
_journal_page_last               6343
_journal_paper_doi               10.1021/jo400760q
_journal_volume                  78
_journal_year                    2013
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C15 H18 O6'
_chemical_formula_sum            'C15 H18 O6'
_chemical_formula_weight         294.29
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-05-03
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr  9 2013 14:06:00, GUI svn.r4458)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 104.774(14)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   7.7724(13)
_cell_length_b                   7.4170(6)
_cell_length_c                   12.6426(13)
_cell_measurement_reflns_used    926
_cell_measurement_temperature    297.10(10)
_cell_measurement_theta_max      24.9340
_cell_measurement_theta_min      3.8550
_cell_volume                     704.72(16)
_computing_cell_refinement
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics
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O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
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O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      297.10(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9974
_diffrn_measured_fraction_theta_max 0.8913
_diffrn_measurement_details
;
  1 omega  -97.00  -55.00   1.5000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.2137  178.0000 -150.0000 28

  2 omega   -2.00   85.00   1.5000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       22.8075   57.0000  150.0000 58

  3 omega  -10.00   86.00   1.5000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       22.8075   38.0000  -90.0000 64
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0561544000
_diffrn_orient_matrix_UB_12      0.0217692000
_diffrn_orient_matrix_UB_13      -0.0520472000
_diffrn_orient_matrix_UB_21      -0.0754867000
_diffrn_orient_matrix_UB_22      -0.0257896000
_diffrn_orient_matrix_UB_23      0.0181975000
_diffrn_orient_matrix_UB_31      -0.0081364000
_diffrn_orient_matrix_UB_32      0.0895243000
_diffrn_orient_matrix_UB_33      0.0179328000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0167
_diffrn_reflns_av_unetI/netI     0.0524
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       6
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            2647
_diffrn_reflns_theta_full        25.50
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.21
_diffrn_source                   'SuperNova (Mo) x-ray Source'
_exptl_absorpt_coefficient_mu    0.107
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82855
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.387
_exptl_crystal_description       plate
_exptl_crystal_F_000             312
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.177
_refine_diff_density_min         -0.164
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.2(16)
_refine_ls_extinction_coef       0.023(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     195
_refine_ls_number_reflns         2294
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0689
_refine_ls_R_factor_gt           0.0475
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0448P)^2^+0.0021P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0989
_refine_ls_wR_factor_ref         0.1137
_reflns_number_gt                1715
_reflns_number_total             2294
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo400760q_si_002.cif
_cod_data_source_block           fangbw0502
_cod_original_cell_volume        704.73(15)
_cod_database_code               4028350
_reflns_odcompleteness_completeness 99.74
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
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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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C8(H8), C9(H9), C11(H11)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C13(H13A,H13B), C14(H14A,H14B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6)
2.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C15(H15A,H15B,H15C)
2.e Idealised tetrahedral OH refined as rotating group:
 O3(H3), O4(H4)
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