Assembly of the Limonoid Architecture by a Divergent Approach: Total Synthesis of (±)-Andirolide N via (±)-8α-Hydroxycarapin.
Schuppe, Alexander W.; Newhouse, Timothy R.; Journal of the American Chemical Society 139 (2017) 631–634; doi:10.1021/jacs.6b12268

data_4125744
_publ_contact_author
;
 Prof. Timothy R. Newhouse         
 The Department of Chemistry 
 Yale University 
 P. O. Box 208107 
 New Haven 
 Connecticut 06520 USA.
;
_publ_section_title
;
 Assembly of the Limonoid Architecture by a Divergent Approach: Total
 Synthesis of (+-)-Andirolide N via (+-)-8\a-Hydroxycarapin.
;
_journal_issue                   2
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              631
_journal_page_last               634
_journal_paper_doi               10.1021/jacs.6b12268
_journal_volume                  139
_journal_year                    2017
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C19 H20 O4'
_chemical_formula_sum            'C19 H20 O4'
_chemical_formula_weight         312.35
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_symmetry_space_group_name_Hall  'P 2c -2ac'
_symmetry_space_group_name_H-M   'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.3242(3)
_cell_length_b                   6.37560(10)
_cell_length_c                   28.920(2)
_cell_measurement_reflns_used    78832
_cell_measurement_temperature    93(2)
_cell_measurement_theta_max      68.3
_cell_measurement_theta_min      2.7
_cell_volume                     3009.9(2)
_computing_cell_refinement       'CrystalClear-SM Expert 2.0 r15 (Rigaku, 2011)'
_computing_data_collection       'CrystalClear-SM Expert 2.0 r15 (Rigaku, 2011)'
_computing_data_reduction        'CrystalClear-SM Expert 2.0 r15 (Rigaku, 2011)'
_computing_molecular_graphics
;
Dolomanov, O.V.; Bourhis, L.J.; Gildea, R.J.; Howard, J.A.K.; Puschmann, H., 
OLEX2: A complete structure solution, refinement and analysis program
(2009). J. Appl. Cryst., 42, 339-341.
;
_computing_publication_material  'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXS-2013 (Sheldrick, 2013)'
_diffrn_ambient_temperature      93(2)
_diffrn_detector_area_resol_mean 22.2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Rigaku Saturn 944+ CCD'
_diffrn_measurement_method       \w
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54187
_diffrn_reflns_av_R_equivalents  0.1467
_diffrn_reflns_av_unetI/netI     0.0813
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            86251
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.687
_diffrn_reflns_theta_max         68.243
_diffrn_reflns_theta_min         3.056
_diffrn_source                   'Rotating Anode'
_exptl_absorpt_coefficient_mu    0.781
_exptl_absorpt_correction_T_max  0.969
_exptl_absorpt_correction_T_min  0.822
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Jacobson, R. (1998) Private Communication'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.379
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Block
_exptl_crystal_F_000             1328
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.040
_refine_diff_density_max         0.449
_refine_diff_density_min         -0.207
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
; 
 Refined as an inversion twin.

 Refinement of F^2^ against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F^2^, conventional R-factors R are based 
 on F, with F set to zero for negative F^2^. The threshold expression of 
 F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F^2^ are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 

 The hydrogen atoms were first found in the difference map, then generated 
 geometrically and refined as riding atoms with C-H distances = 0.95- 0.99 
 \%A and U~iso~(H) = 1.2 times U~eq~(C) for CH and CH2 groups and U~iso~(H) 
 = 1.5 times U~eq~(C) for CH3 groups. 
;
_refine_ls_abs_structure_Flack   0.1(3)
_refine_ls_extinction_coef       0.0016(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   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     421
_refine_ls_number_reflns         5495
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0523
_refine_ls_R_factor_gt           0.0486
_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^)+(0.0719P)^2^+0.7520P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1289
_refine_ls_wR_factor_ref         0.1329
_reflns_Friedel_coverage         0.957
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                5039
_reflns_number_total             5495
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b12268_si_002.cif
_cod_data_source_block           007-14181
_cod_database_code               4125744
_shelx_estimated_absorpt_t_min   0.859
_shelx_estimated_absorpt_t_max   0.969
_shelxl_version_number           2014-3
_shelx_res_checksum              91338
_shelx_hkl_checksum              36341