Regiodivergent Photocyclization of Dearomatized Acylphloroglucinols: Asymmetric Syntheses of (-)-Nemorosone and (-)-6-<i>epi</i>-Garcimultiflorone A.
Wen, Saishuai; Boyce, Jonathan H.; Kandappa, Sunil K.; Sivaguru, Jayaraman; Porco, Jr, John A; Journal of the American Chemical Society 141 (2019) 11315–11321; doi:10.1021/jacs.9b05600

data_4127413
_publ_section_title
;
 Regiodivergent Photocyclization of Dearomatized Acylphloroglucinols:
 Asymmetric Syntheses of (-)-Nemorosone and
 (-)-6-<i>epi</i>-Garcimultiflorone A.
;
_journal_issue                   28
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11315
_journal_page_last               11321
_journal_paper_doi               10.1021/jacs.9b05600
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration rmad
_chemical_formula_moiety         '1(C29 H33 O4), C12 H24 N'
_chemical_formula_sum            'C41 H57 N O4'
_chemical_formula_weight         627.87
_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
_audit_creation_date             2019-04-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-04-18 # Formatted by publCIF

;
_cell_angle_alpha                90
_cell_angle_beta                 129.951(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   33.1205(10)
_cell_length_b                   11.3921(3)
_cell_length_c                   25.2617(13)
_cell_measurement_reflns_used    9835
_cell_measurement_temperature    100(1)
_cell_measurement_theta_max      66.32
_cell_measurement_theta_min      2.28
_cell_volume                     7306.8(5)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2016)'
_computing_data_collection       'APEX2 (Bruker, 2016)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2016)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100(1)
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker X8 Proteum-R'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  Montel
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0557
_diffrn_reflns_av_unetI/netI     0.0359
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       39
_diffrn_reflns_limit_h_min       -39
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            89574
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        66.782
_diffrn_reflns_theta_max         66.782
_diffrn_reflns_theta_min         2.281
_diffrn_source                   'rotating anode'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.560
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.6591
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0803 before and 0.0660 after correction.
The Ratio of minimum to maximum transmission is 0.8755.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.142
_exptl_crystal_description       plate
_exptl_crystal_F_000             2736
_exptl_crystal_size_max          0.118
_exptl_crystal_size_mid          0.102
_exptl_crystal_size_min          0.036
_refine_diff_density_max         0.245
_refine_diff_density_min         -0.243
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details
;
 Flack x determined using 4686 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     880
_refine_ls_number_reflns         12802
_refine_ls_number_restraints     27
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0492
_refine_ls_R_factor_gt           0.0411
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0634P)^2^+2.1555P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1042
_refine_ls_wR_factor_ref         0.1095
_reflns_Friedel_coverage         0.883
_reflns_Friedel_fraction_full    0.980
_reflns_Friedel_fraction_max     0.980
_reflns_number_gt                11261
_reflns_number_total             12802
_reflns_threshold_expression     'I > 2\s(I)'
_publcif_datablock.id            {24bc8466-9bf5-480d-9e7e-1ffa8dfe9bfc}
_cod_data_source_file            ja9b05600_si_002.cif
_cod_data_source_block           wen4_mono
_cod_database_code               4127413
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H23B,H23A,H23C} of C23B, All C(H,H) groups, All N(H,H)
  groups
 At 1.5 times of:
  {H25D,H25E,H25F} of C25A, {H10A,H10B,H10C} of C10B, {H11A,H11B,H11C} of
  C11B, {H25A,H25B,H25C} of C25B, {H11D,H11E,H11F} of C11A, {H10D,H10E,H10F} of
  C10A
2. Restrained distances
 C29B-C28B = C28C-C29C = C29D-C28D
 1.31 with sigma of 0.02
 C27C-C23B = C27B-C23B = C27D-C23B
 1.54 with sigma of 0.02
 C27D-C28D = C28C-C27C = C28B-C27B
 1.54 with sigma of 0.02
 C4B-C2B = C23B-C28B
 2.5 with sigma of 0.04
 C23B-C28C
 2.5 with sigma of 0.04
 C23B-C28D
 2.5 with sigma of 0.04
 C27B-C29B
 2.5 with sigma of 0.04
 C27C-C29C
 2.5 with sigma of 0.04
 C27D-C29D
 2.5 with sigma of 0.04
 C27D-C23B \\sim C27B-C23B \\sim C27C-C23B
 with sigma of 0.02
 C28D-C27D \\sim C28C-C27C \\sim C28B-C27B
 with sigma of 0.02
 C29B-C28B \\sim C29C-C28C \\sim C29D-C28D
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C27D) = Uanis(C27B) = Uanis(C27C)
4. Others
 1*[Sof(H23B)+Sof(C27B)+Sof(H27A)+Sof(H27B)+Sof(C28B)+Sof(H28B)+Sof(C29B)+
 Sof(H29A)+Sof(H29B)]+1*[Sof(H23A)+Sof(C29C)+Sof(H29C)+Sof(H29D)+Sof(C28C)+
 Sof(H28C)+Sof(C27C)+Sof(H27C)+Sof(H27D)]+1*[Sof(H23C)+Sof(C28D)+Sof(H28D)+
 Sof(C29D)+Sof(H29E)+Sof(H29F)+Sof(C27D)+Sof(H27E)+Sof(H27F)]=1 with esd of
 0.001
 Sof(H23B)=Sof(C27B)=Sof(H27A)=Sof(H27B)=Sof(C28B)=Sof(H28B)=Sof(C29B)=
 Sof(H29A)=Sof(H29B)=FVAR(1)
 Sof(H23A)=Sof(C29C)=Sof(H29C)=Sof(H29D)=Sof(C28C)=Sof(H28C)=Sof(C27C)=
 Sof(H27C)=Sof(H27D)=FVAR(2)
 Sof(H23C)=Sof(C28D)=Sof(H28D)=Sof(C29D)=Sof(H29E)=Sof(H29F)=Sof(C27D)=
 Sof(H27E)=Sof(H27F)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C4N(H4N), C7N(H7N), C4B(H4B), C7M(H7M), C4M(H4M), C23B(H23B), C23B(H23A),
 C23B(H23C), C23A(H23D), C4A(H4A)
5.b Secondary CH2 refined with riding coordinates:
 N1N(H1NA,H1NB), N1M(H1MA,H1MB), C12N(H12A,H12B), C22B(H22A,H22B), C5N(H5NA,
 H5NB), C11N(H11G,H11H), C5B(H5BA,H5BB), C8M(H8MA,H8MB), C12M(H12C,H12D),
 C3N(H3NA,H3NB), C2N(H2NA,H2NB), C5A(H5AA,H5AB), C3B(H3BA,H3BB), C8N(H8NA,H8NB),
  C10N(H10G,H10H), C3M(H3MA,H3MB), C5M(H5MA,H5MB), C9N(H9NA,H9NB), C6N(H6NA,
 H6NB), C9M(H9MA,H9MB), C1N(H1NC,H1ND), C22A(H22C,H22D), C2M(H2MA,H2MB),
 C10M(H10I,H10J), C1M(H1MC,H1MD), C11M(H11I,H11J), C6M(H6MA,H6MB), C27B(H27A,
 H27B), C3A(H3AA,H3AB), C27A(H27G,H27H), C27C(H27C,H27D), C27D(H27E,H27F)
5.c Aromatic/amide H refined with riding coordinates:
 C20B(H20B), C20A(H20A), C18B(H18B), C14A(H14A), C2B(H2B), C14B(H14B),
 C15A(H15A), C17B(H17B), C16B(H16B), C18A(H18A), C15B(H15B), C17A(H17A),
 C16A(H16A), C28A(H28A), C2A(H2A), C28B(H28B), C28C(H28C), C28D(H28D)
5.d X=CH2 refined with riding coordinates:
 C1B(H1BA,H1BB), C26A(H26C,H26D), C26B(H26A,H26B), C29A(H29G,H29H), C1A(H1AA,
 H1AB), C29B(H29A,H29B), C29C(H29C,H29D), C29D(H29E,H29F)
5.e Idealised Me refined as rotating group:
 C10B(H10A,H10B,H10C), C11A(H11D,H11E,H11F), C11B(H11A,H11B,H11C), C10A(H10D,
 H10E,H10F), C25B(H25A,H25B,H25C), C25A(H25D,H25E,H25F)
;
_shelx_res_checksum              64032
_shelx_hkl_checksum              93534
_olex2_submission_special_instructions 'No special instructions were received'