Total Syntheses of the Coumarin-Containing Natural Products Pimpinellin and Fraxetin Using Au(I)-Catalyzed Intramolecular Hydroarylation (IMHA) Chemistry
Aymeric Cervi; Paul Aillard; Nourallah Hazeri; Laurent Petit; Christina L. L. Chai; Anthony C. Willis; Martin G. Banwell; Journal of Organic Chemistry 78 (2013) 9876–9882; doi:10.1021/jo401583q

data_4028647
_publ_contact_author_address
;
Research School of Chemistry,
Australian National University,
Canberra, A. C. T. 0200, Australia
;
_publ_contact_author_email       'mgb@rsc.anu.edu.au '
_publ_contact_author_fax         ' 61 2 6125 8114 '
_publ_contact_author_name        'Martin G. Banwell'
_publ_contact_author_phone       ' 61 2 6125 8202 '
_publ_section_title
;
 Total Syntheses of the Coumarin-Containing Natural Products Pimpinellin
 and Fraxetin Using Au(I)-Catalyzed Intramolecular Hydroarylation (IMHA)
 Chemistry
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              9876
_journal_page_last               9882
_journal_paper_doi               10.1021/jo401583q
_journal_volume                  78
_journal_year                    2013
_chemical_compound_source        local
_chemical_formula_moiety         'C13 H20 O4'
_chemical_formula_sum            'C13 H20 O4'
_chemical_formula_weight         240.30
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2yab'
_symmetry_space_group_name_H-M   'P 1 21/a 1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_audit_creation_date             13-05-16
_audit_creation_method           CRYSTALS_ver_14.40
_audit_update_record
;
2013-05-17 - Report on C13 H20 O4 
             by Anthony C. Willis
             for Aymeric Cervi and Martin Banwell

2013-05-17 - passes checkcif tests with a few warnings  
;
_cell_angle_alpha                90
_cell_angle_beta                 99.797(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.7674(3)
_cell_length_b                   6.7691(2)
_cell_length_c                   16.1154(5)
_cell_measurement_reflns_used    22405
_cell_measurement_temperature    200
_cell_measurement_theta_max      27.5
_cell_measurement_theta_min      2.6
_cell_volume                     1372.44(7)
_computing_cell_refinement       'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_computing_data_collection       'COLLECT (Nonius, 2001).'
_computing_data_reduction        'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_computing_molecular_graphics
;  
ORTEP-II (Johnson 1976) in teXsan (MSC, 1992-1997) 
;
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'SIR92 (Altomare et al., 1994)'
_diffrn_ambient_temperature      200
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Nonius KappaCCD'
_diffrn_measurement_method       ' \f and \w scans with CCD '
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.055
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            27843
_diffrn_reflns_theta_full        27.477
_diffrn_reflns_theta_max         27.477
_diffrn_reflns_theta_min         2.565
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.085
_exptl_absorpt_correction_T_max  0.995
_exptl_absorpt_correction_T_min  0.974
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details
;
via gaussian method (Coppens, 1970) implemented in maXus (2000)
;
_exptl_crystal_colour            'pale yellow'
_exptl_crystal_density_diffrn    1.163
_exptl_crystal_description       plate
_exptl_crystal_F_000             520.000
_exptl_crystal_size_max          0.470
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.060
_refine_diff_density_max         0.23
_refine_diff_density_min         -0.33
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.0458
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     186
_refine_ls_number_reflns         3145
_refine_ls_number_restraints     15
_refine_ls_R_factor_all          0.0730
_refine_ls_R_factor_gt           0.0554
_refine_ls_shift/su_max          0.0175536
_refine_ls_shift/su_mean         0.0012803
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.05P)^2^ + 0.61P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.1298
_refine_ls_wR_factor_gt          0.1209
_refine_ls_wR_factor_ref         0.1298
_reflns_limit_h_max              16
_reflns_limit_h_min              -16
_reflns_limit_k_max              8
_reflns_limit_k_min              0
_reflns_limit_l_max              20
_reflns_limit_l_min              0
_reflns_number_gt                2458
_reflns_number_total             3146
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   3.18
_oxford_diffrn_Wilson_scale      1.25
_oxford_refine_ls_r_factor_ref   0.0730
_oxford_refine_ls_scale          0.958(4)
_oxford_reflns_number_all        3145
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_oxford_structure_analysis_title 'ban1326 At 16:56 on 15/ 5'
_cod_data_source_file            jo401583q_si_004.cif
_cod_data_source_block           ban1326
_cod_original_sg_symbol_H-M      'P 1 21/a 1 '
_cod_database_code               4028647
_iucr_refine_instruction_details_constraints
;
BLOCK SCALE X'S, O(1,U'S) UNTIL C(13) C(8,OCC) UNTIL C(9) 
CONT C(10,OCC) UNTIL C(12) 
CONT C(81,U'S,OCC) UNTIL C(91) 
CONT C(101,U[ISO],OCC) UNTIL C(121) 
CONT H(1,X'S) 
EQUIV C(8,OCC) UNTIL C(9) C(81,OCC) UNTIL C(91) 
WEIGHT -1 C(81,OCC) UNTIL C(91) 
EQUIV C(10,OCC) UNTIL  C(12) C(101,OCC) UNTIL C(121) 
WEIGHT -1 C(101,OCC) UNTIL C(121) 
FIX C(101,U[ISO]) UNTIL C(121) 
RIDE C   (   5,X'S) H   (  51,X'S) 
RIDE C   (   6,X'S) H   (  61,X'S) 
RIDE C   (   7,X'S) H   (  71,X'S) H(72,X'S) 
RIDE C   (   8,X'S) H   (  81,X'S) H   (  82,X'S) H   (  83,X'S) 
RIDE C   (   9,X'S) H   (  91,X'S) H   (  92,X'S) H   (  93,X'S) 
RIDE C   (  10,X'S) H   ( 101,X'S) 
RIDE C   (  11,X'S) H   ( 111,X'S) H   ( 112,X'S) H   ( 113,X'S) 
RIDE C   (  12,X'S) H   ( 121,X'S) H   ( 122,X'S) H   ( 123,X'S) 
RIDE C   (  13,X'S) H   ( 131,X'S) H   ( 132,X'S) H   ( 133,X'S) 
RIDE C   (   81,X'S) H   (  811,X'S) H   (  812,X'S) H   (  813,X'S) 
RIDE C   (   91,X'S) H   (  911,X'S) H   (  912,X'S) H   (  913,X'S) 
RIDE C(101,X'S) H(1011,X'S) 
RIDE C(111,X'S) H(1111,X'S) H(1112,X'S) H(1113,X'S) 
RIDE C(121,X'S) H(1211,X'S) H(1212,X'S) H(1213,X'S) 
END                                                                             
;
_iucr_refine_instruction_details_restraints
;
DIST 1.50, .02 = C(7) TO C(81), C(7) TO C(91) 
ANGLE 108, 2 = O(2) TO C(7) TO C(81), O(2) TO C(7) TO C(91) 
ANGLE 114, 2 = C(81) TO C(7) TO C(91) 
REM 
VIBR 0.0, .01 = C(8) TO C(81), C(9) TO C(91) 
VIBR 0.0, .01 = C(7) TO C(81), C(7) TO C(91) 
REM 
DIST 1.47, .02 = O(3) TO C(101) 
DIST 1.50, .02 = C(101) TO C(111), C(101) TO C(121) 
ANGLE 108, 2 = O(3) TO C(101) TO C(111), O(3) TO C(101) TO C(121) 
ANGLE 112, 2 = C(111) TO C(101) TO C(121) 
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
END                                                                             
;