Asymmetric Total Synthesis of (+)-Dihydroitomanallene B and Formal Synthesis of (-)-Kumausallene
Fernandes, Rodney Agustinho; Kumar, Atul; Pathare, Ramdas Shivaji; Chemical Communications  (2022) –; doi:10.1039/D2CC04574E

data_7130777
_publ_section_title
;
 Asymmetric Total Synthesis of (+)-Dihydroitomanallene B and Formal
 Synthesis of (-)-Kumausallene
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC04574E
_journal_year                    2022
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C22 H19.52 N2 O9'
_chemical_formula_sum            'C22 H19.52 N2 O9'
_chemical_formula_weight         455.92
_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'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-07-13
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2022-07-13 deposited with the CCDC.	2022-09-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.720(18)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.892(2)
_cell_length_b                   4.6144(5)
_cell_length_c                   16.629(2)
_cell_measurement_reflns_used    3133
_cell_measurement_temperature    150
_cell_measurement_theta_max      30.7460
_cell_measurement_theta_min      2.4590
_cell_volume                     1038.0(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -110.00  70.00   1.00   16.00    --  -20.00   0.00 108.00  180
  2  \w    -66.00   7.00   1.00   16.00    --  -20.00 -72.00  36.00   73
  3  \w   -110.00  53.00   1.00   16.00    --  -20.00   0.00  36.00  163
  4  \w    -69.00  12.00   1.00   16.00    --  -20.00 -72.00 -36.00   81
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0819
_diffrn_reflns_av_unetI/netI     0.1167
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            9785
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        24.994
_diffrn_reflns_theta_max         24.994
_diffrn_reflns_theta_min         2.405
_exptl_absorpt_coefficient_mu    0.115
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91599
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.459
_exptl_crystal_description       plate
_exptl_crystal_F_000             475
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.232
_refine_diff_density_min         -0.263
_refine_diff_density_rms         0.062
_refine_ls_abs_structure_details
;
 Flack x determined using 540 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.9(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.009
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     318
_refine_ls_number_reflns         3601
_refine_ls_number_restraints     26
_refine_ls_restrained_S_all      1.008
_refine_ls_R_factor_all          0.1155
_refine_ls_R_factor_gt           0.0645
_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^)+(0.0355P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1046
_refine_ls_wR_factor_ref         0.1347
_reflns_Friedel_coverage         0.730
_reflns_Friedel_fraction_full    0.958
_reflns_Friedel_fraction_max     0.958
_reflns_number_gt                2199
_reflns_number_total             3601
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc04574e2.cif
_cod_data_source_block           raf-ram-040_mo
_cod_database_code               7130777
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.998
_shelx_estimated_absorpt_t_min   0.977
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C00X-C00W
 1.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C00X) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C00Y) \\sim Ueq, Uanis(C00W)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.001
4. Others
 Sof(H00V)=Sof(C1)=Sof(H1)=1-FVAR(1)
 Sof(C00W)=Sof(H00W)=FVAR(1)
 Sof(C00Y)=Sof(H00N)=Sof(H00T)=1-FVAR(2)
 Sof(C00X)=Sof(H00I)=Sof(H00J)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C00K(H00K), C00S(H00S), C00V(H00V)
5.b Secondary CH2 refined with riding coordinates:
 C00H(H00B,H00C), C00J(H00D,H00E), C00T(H00G,H00H)
5.c Aromatic/amide H refined with riding coordinates:
 C00A(H00A), C00F(H00F), C00L(H00L), C00M(H00M), C00O(H00O), C00P(H00P),
 C00Q(H00Q), C00R(H00R), C00W(H00W), C1(H1)
5.d X=CH2 refined with riding coordinates:
 C00X(H00I,H00J), C00Y(H00N,H00T)
;
_shelx_res_checksum              91849
_shelx_hkl_checksum              18756
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;