Asymmetric Total Synthesis of the Indole Diterpene Alkaloid Paspaline.
Sharpe, Robert J.; Johnson, Jeffrey S.; The Journal of organic chemistry 80 (2015) 9740–9766; doi:10.1021/acs.joc.5b01844

data_4036409
_publ_section_title
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 Asymmetric Total Synthesis of the Indole Diterpene Alkaloid Paspaline.
;
_journal_issue                   19
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              9740
_journal_page_last               9766
_journal_paper_doi               10.1021/acs.joc.5b01844
_journal_volume                  80
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H30 O3'
_chemical_formula_sum            'C18 H30 O3'
_chemical_formula_weight         294.42
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2014-05-15
_audit_creation_method
;
Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   6.2753(2)
_cell_length_b                   14.5021(4)
_cell_length_c                   36.3418(11)
_cell_measurement_reflns_used    4919
_cell_measurement_temperature    100
_cell_measurement_theta_max      66.41
_cell_measurement_theta_min      2.43
_cell_volume                     3307.29(17)
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    'olex2.solve (Bourhis et al., 2013)'
_diffrn_ambient_temperature      100.
_diffrn_measured_fraction_theta_full 0.961
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0785
_diffrn_reflns_av_unetI/netI     0.0666
_diffrn_reflns_Laue_measured_fraction_full 0.961
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            20015
_diffrn_reflns_point_group_measured_fraction_full 0.957
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         66.587
_diffrn_reflns_theta_min         2.431
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.617
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8720
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0697 before and 0.0639 after correction.
The Ratio of minimum to maximum transmission is 0.8720.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.183
_exptl_crystal_description       needle
_exptl_crystal_F_000             1296
_exptl_crystal_size_max          0.267
_exptl_crystal_size_mid          0.147
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.208
_refine_diff_density_min         -0.177
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 1559 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.0(2)
_refine_ls_extinction_coef       0.00071(16)
_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   1.011
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     396
_refine_ls_number_reflns         5737
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.0740
_refine_ls_R_factor_gt           0.0512
_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^)+(0.0592P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1119
_refine_ls_wR_factor_ref         0.1236
_reflns_Friedel_coverage         0.725
_reflns_Friedel_fraction_full    0.951
_reflns_Friedel_fraction_max     0.976
_reflns_number_gt                4468
_reflns_number_total             5737
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo5b01844_si_002.cif
_cod_data_source_block           x1405008
_cod_database_code               4036409
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.952
_shelx_estimated_absorpt_t_min   0.853
_olex2_refinement_description
;
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
2.a Ternary CH refined with riding coordinates:
 C4(H4A), C5(H5), C13(H13), C22(H22), C23(H23), C31(H31)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B),
 C15(H15A,H15B), C16(H16A,H16B), C24(H24A,H24B), C25(H25A,H25B), C28(H28A,H28B),
  C29(H29A,H29B), C30(H30A,H30B), C33(H33A,H33B), C34(H34A,H34B)
2.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C35(H35A,H35B,H35C), C36(H36A,H36B,
 H36C)
;
_shelx_res_checksum              91934
_shelx_hkl_checksum              91841