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_4127412
_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 rm
_chemical_formula_moiety         'C27 H29 O4, C12 H24 N, 0.87(C H Cl3)'
_chemical_formula_sum            'C39.87 H53.87 Cl2.62 N O4'
_chemical_formula_weight         704.09
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-03-20
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_audit_update_record
;
2018-03-20 # Formatted by publCIF

;
_cell_angle_alpha                90
_cell_angle_beta                 97.966(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.3691(5)
_cell_length_b                   17.1035(8)
_cell_length_c                   11.0229(5)
_cell_measurement_reflns_used    9447
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      66.44
_cell_measurement_theta_min      4.05
_cell_volume                     1936.02(16)
_computing_cell_refinement       'SAINT V8.38A (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 (Sheldrick, 2015)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.988
_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  0.0510
_diffrn_reflns_av_unetI/netI     0.0272
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            64642
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.217
_diffrn_reflns_theta_max         67.217
_diffrn_reflns_theta_min         4.049
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.206
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.5890
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1286 before and 0.0812 after correction.
The Ratio of minimum to maximum transmission is 0.7824.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.208
_exptl_crystal_description       block
_exptl_crystal_F_000             753
_exptl_crystal_size_max          0.376
_exptl_crystal_size_mid          0.119
_exptl_crystal_size_min          0.081
_refine_diff_density_max         0.367
_refine_diff_density_min         -0.184
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
;
 Flack x determined using 3008 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.060(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     515
_refine_ls_number_reflns         6845
_refine_ls_number_restraints     807
_refine_ls_restrained_S_all      1.010
_refine_ls_R_factor_all          0.0437
_refine_ls_R_factor_gt           0.0420
_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^)+(0.0770P)^2^+0.3760P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1177
_refine_ls_wR_factor_ref         0.1193
_reflns_Friedel_coverage         0.924
_reflns_Friedel_fraction_full    0.982
_reflns_Friedel_fraction_max     0.982
_reflns_number_gt                6555
_reflns_number_total             6845
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b05600_si_001.cif
_cod_data_source_block           wen3_0m
_cod_database_code               4127412
_publcif_datablock.id            {bdaf2ecb-315b-4882-8e62-a106cd2359d6}
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{C1SA, C1SB}
3. Restrained distances
 C1SB-Cl1B
 1.75 with sigma of 0.02
 Cl2C-C1SC
 1.7 with sigma of 0.02
 Cl1C-C1SC
 1.7 with sigma of 0.02
 Cl3C-C1SC
 1.7 with sigma of 0.02
 C1SD-Cl1D
 1.7 with sigma of 0.02
 C1SD-Cl2D
 1.7 with sigma of 0.02
 Cl3B-C1SB = Cl2A-C1SA = Cl2B-C1SB = Cl1A-C1SA = Cl3A-C1SA
 1.75 with sigma of 0.02
 C1SD-Cl3D
 1.7 with sigma of 0.02
 C27A-C26A
 1.3 with sigma of 0.02
 C26A-C27B
 1.3 with sigma of 0.02
 C26B-C25
 1.45 with sigma of 0.02
 C25-C26B
 1.4 with sigma of 0.02
 C26B-C27B
 1.3 with sigma of 0.02
 Cl1C-Cl2C
 2.8 with sigma of 0.04
 Cl2C-Cl3C
 2.8 with sigma of 0.04
 Cl3C-Cl1C
 2.8 with sigma of 0.04
 Cl2D-Cl1D
 2.7 with sigma of 0.04
 Cl3D-Cl2D
 2.7 with sigma of 0.04
 Cl1D-Cl3D
 2.7 with sigma of 0.04
 C27A-C25
 2.49 with sigma of 0.04
 C27B-C25
 2.49 with sigma of 0.04
 C26A-C23
 2.54 with sigma of 0.04
 C26B-C23
 2.54 with sigma of 0.04
4. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(C1SB) \\sim Ueq, Uanis(C1SA) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C1SB) = Uanis(C1SA) = Uanis(C1SC)
Uanis(Cl2B) = Uanis(Cl1A)
Uanis(Cl3D) = Uanis(Cl3A)
Uanis(Cl1D) = Uanis(Cl2C)
Uanis(Cl2D) = Uanis(Cl3B)
Uanis(Cl3C) = Uanis(C1SA)
Uanis(C1SD) = Uanis(C1SA)
6. Others
 Sof(Cl2B)=Sof(Cl1B)=Sof(Cl3B)=Sof(C1SB)=Sof(H1SB)=FVAR(1)
 Sof(Cl3A)=Sof(Cl2A)=Sof(C1SA)=Sof(H1SA)=Sof(Cl1A)=FVAR(2)
 Sof(Cl3C)=Sof(Cl1C)=Sof(Cl2C)=Sof(C1SC)=Sof(H1SC)=FVAR(3)
 Sof(H25C)=Sof(H25D)=Sof(C27B)=Sof(H27C)=Sof(H27D)=Sof(C26B)=Sof(H26B)=1-FVAR(4)
 Sof(H25A)=Sof(H25B)=Sof(C27A)=Sof(H27A)=Sof(H27B)=Sof(C26A)=Sof(H26A)=FVAR(4)
 Sof(Cl3D)=Sof(Cl2D)=Sof(C1SD)=Sof(H1SD)=Sof(Cl1D)=FVAR(5)
7.a Ternary CH refined with riding coordinates:
 C30(H30), C33(H33), C12(H12), C1SB(H1SB), C1SA(H1SA), C1SC(H1SC), C1SD(H1SD)
7.b Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), C31(H31A,H31B), C38(H38A,H38B), C19(H19A,H19B), C29(H29A,H29B),
 C37(H37A,H37B), C34(H34A,H34B), C16(H16A,H16B), C27(H27E,H27F), C32(H32A,H32B),
  C25(H25A,H25B), C25(H25C,H25D), C35(H35A,H35B), C28(H28A,H28B), C36(H36A,
 H36B), C13(H13A,H13B)
7.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C20(H20), C2(H2), C1(H1), C6(H6), C14(H14), C26A(H26A),
 C26B(H26B)
7.d X=CH2 refined with riding coordinates:
 C21(H21A,H21B), C27A(H27A,H27B), C15(H15A,H15B), C27B(H27C,H27D)
7.e Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C)
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_shelx_res_checksum              35252
_shelx_hkl_checksum              58781
_olex2_submission_special_instructions 'No special instructions were received'
_publcif_funding_html
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;