Total Synthesis of the Galbulimima Alkaloids Himandravine and GB17 Using Biomimetic Diels-Alder Reactions of Double Diene Precursors.
Larson, Reed T.; Pemberton, Ryan P.; Franke, Jenna M.; Tantillo, Dean J.; Thomson, Regan J.; Journal of the American Chemical Society 137 (2015) 11197–11204; doi:10.1021/jacs.5b07710

data_4124294
_publ_section_title
;
 Total Synthesis of the Galbulimima Alkaloids Himandravine and GB17 Using
 Biomimetic Diels-Alder Reactions of Double Diene Precursors.
;
_journal_issue                   34
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11197
_journal_page_last               11204
_journal_paper_doi               10.1021/jacs.5b07710
_journal_volume                  137
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'Cl, C28 H38 N O3, 0.25(C H4 O)'
_chemical_formula_sum            'C28.25 H39 Cl N O3.25'
_chemical_formula_weight         480.05
_chemical_name_systematic
;
 ?
;
_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'
_symmetry_space_group_name_Hall  'C 2y'
_symmetry_space_group_name_H-M   'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-05-02
_audit_creation_method
;
Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.683(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.3133(10)
_cell_length_b                   8.6913(4)
_cell_length_c                   18.1902(13)
_cell_measurement_reflns_used    3267
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      63.618
_cell_measurement_theta_min      4.646
_cell_volume                     3009.9(3)
_computing_cell_refinement       'SAINT V7.23A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2.1-4 (Bruker, 2007)'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.886
_diffrn_measured_fraction_theta_max 0.961
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'MX optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0831
_diffrn_reflns_av_unetI/netI     0.1007
_diffrn_reflns_laue_measured_fraction_full 0.886
_diffrn_reflns_laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            11750
_diffrn_reflns_point_group_measured_fraction_full 0.832
_diffrn_reflns_point_group_measured_fraction_max 0.904
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         64.334
_diffrn_reflns_theta_min         2.464
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    1.324
_exptl_absorpt_correction_T_max  0.7524
_exptl_absorpt_correction_T_min  0.6307
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0936 before and 0.0570 after correction.
The Ratio of minimum to maximum transmission is 0.8383.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.059
_exptl_crystal_description       plate
_exptl_crystal_F_000             1034
_exptl_crystal_size_max          0.184
_exptl_crystal_size_mid          0.131
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.634
_refine_diff_density_min         -0.321
_refine_diff_density_rms         0.097
_refine_ls_abs_structure_details
;
 Flack x determined using 826 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.01(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.006
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     411
_refine_ls_number_reflns         4546
_refine_ls_number_restraints     276
_refine_ls_restrained_S_all      0.980
_refine_ls_R_factor_all          0.1655
_refine_ls_R_factor_gt           0.0996
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2531
_refine_ls_wR_factor_ref         0.3085
_reflns_Friedel_coverage         0.751
_reflns_friedel_fraction_full    0.768
_reflns_friedel_fraction_max     0.838
_reflns_number_gt                2582
_reflns_number_total             4546
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b07710_si_002.cif
_cod_data_source_block           n3406
_cod_depositor_comments
'Adding full bibliography for 4124293--4124295.cif.'
_cod_database_code               4124294
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.793
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 C23-C22 \\sim C23B-C22B \\sim C23A-C22A
 with sigma of 0.01
 O3-C22 \\sim O3-C22B \\sim O3-C22A
 with sigma of 0.01
3. Rigid bond restraints
 C23A, C28A, C27A, C26A, C25A, C24A, C23B, C24B, C25B, C26B, C27B, C28B, C23,
 C24, C25, C26, C27, C28, C22, C22B, C22A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1S, O1S
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C23A \\sim C28A \\sim C27A \\sim C26A \\sim C25A \\sim C24A \\sim C23B \\sim
C24B \\sim C25B \\sim C26B \\sim C27B \\sim C28B \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27 \\sim C28 \\sim C22 \\sim C22B \\sim C22A: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C1S \\sim O1S: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
Uanis(C1S) \\sim Ueq, Uanis(O1S) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.002
5. Others
 1*[Sof(C22B)+Sof(H22E)+Sof(H22F)+Sof(C23B)+Sof(C24B)+Sof(H24B)+Sof(C25B)+
 Sof(H25B)+Sof(C26B)+Sof(H26B)+Sof(C27B)+Sof(H27B)+Sof(C28B)+Sof(H28B)]+1*
 [Sof(C22A)+Sof(H22C)+Sof(H22D)+Sof(C23A)+Sof(C24A)+Sof(H24A)+Sof(C25A)+
 Sof(H25A)+Sof(C26A)+Sof(H26A)+Sof(C27A)+Sof(H27A)+Sof(C28A)+Sof(H28A)]+1*
 [Sof(C22)+Sof(H22A)+Sof(H22B)+Sof(C26)+Sof(H26)+Sof(C25)+Sof(H25)+Sof(C24)+
 Sof(H24)+Sof(C23)+Sof(C28)+Sof(H28)+Sof(C27)+Sof(H27)]=1 with esd of 0.0001
 Sof(C22B)=Sof(H22E)=Sof(H22F)=Sof(C23B)=Sof(C24B)=Sof(H24B)=Sof(C25B)=
 Sof(H25B)=Sof(C26B)=Sof(H26B)=Sof(C27B)=Sof(H27B)=Sof(C28B)=Sof(H28B)=FVAR(1)
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(C26)=Sof(H26)=Sof(C25)=Sof(H25)=Sof(C24)=
 Sof(H24)=Sof(C23)=Sof(C28)=Sof(H28)=Sof(C27)=Sof(H27)=FVAR(2)
 Sof(C22A)=Sof(H22C)=Sof(H22D)=Sof(C23A)=Sof(C24A)=Sof(H24A)=Sof(C25A)=
 Sof(H25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(H28A)=FVAR(3)
 Fixed Sof: O1S(0.25) H1S(0.25) C1S(0.25) H1SA(0.25) H1SB(0.25) H1SC(0.25)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C5(H5), C7(H7), C10(H10), C13(H13), C16(H16), C20(H20)
6.b Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), C4(H4A,H4B), C6(H6A,H6B), C8(H8A,H8B), C9(H9A,H9B), C17(H17A,
 H17B), C18(H18A,H18B), C19(H19A,H19B), C22(H22A,H22B), C22A(H22C,H22D),
 C22B(H22E,H22F)
6.c Me refined with riding coordinates:
 C1S(H1SA,H1SB,H1SC)
6.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C14(H14), C26(H26), C25(H25), C24(H24), C28(H28), C27(H27),
 C24A(H24A), C25A(H25A), C26A(H26A), C27A(H27A), C28A(H28A), C24B(H24B),
 C25B(H25B), C26B(H26B), C27B(H27B), C28B(H28B)
6.e Fitted hexagon refined as free rotating group:
 C26(C25,C24,C23,C28,C27), C23A(C24A,C25A,C26A,C27A,C28A), C23B(C24B,C25B,C26B,
 C27B,C28B)
6.f Tetrahedral OH refined with riding coordinates:
 O1S(H1S)
6.g Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C21(H21A,H21B,H21C)
;
_shelx_res_checksum              24702
_shelx_hkl_checksum              39391