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\psz1\linex0\headery851\footery992\colsx425\endnhere\sectlinegrid360\sectspecifyl {\footer \pard\plain \s20\qc \li0\ri0\nowidctlpar\tqc\tx4252\tqr\tx8504\aspalpha\aspnum\faauto\nosnaplinegrid\adjustright\rin0\lin0\itap0 \fs21\lang1033\langfe1041\kerning2\loch\af26\hich\af26\dbch\af23\cgrid\langnp1033\langfenp1041 {\field{\*\fldinst {\cs21 \hich\af26\dbch\af23\loch\f26 PAGE }}{\fldrslt {\cs21\lang1024\langfe1024\noproof \hich\af26\dbch\af23\loch\f26 3}}}{ \par }}{\*\pnseclvl1\pnucrm\pnstart1\pnindent720\pnhang{\pntxta \dbch .}}{\*\pnseclvl2\pnucltr\pnstart1\pnindent720\pnhang{\pntxta \dbch .}}{\*\pnseclvl3\pndec\pnstart1\pnindent720\pnhang{\pntxta \dbch .}}{\*\pnseclvl4\pnlcltr\pnstart1\pnindent720\pnhang {\pntxta \dbch )}}{\*\pnseclvl5\pndec\pnstart1\pnindent720\pnhang{\pntxtb \dbch (}{\pntxta \dbch )}}{\*\pnseclvl6\pnlcltr\pnstart1\pnindent720\pnhang{\pntxtb \dbch (}{\pntxta \dbch )}}{\*\pnseclvl7\pnlcrm\pnstart1\pnindent720\pnhang{\pntxtb \dbch (} {\pntxta \dbch )}}{\*\pnseclvl8\pnlcltr\pnstart1\pnindent720\pnhang{\pntxtb \dbch (}{\pntxta \dbch )}}{\*\pnseclvl9\pnlcrm\pnstart1\pnindent720\pnhang{\pntxtb \dbch (}{\pntxta \dbch )}}\pard\plain \qc \li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0 \fs21\lang1033\langfe1041\kerning2\loch\af26\hich\af26\dbch\af23\cgrid\langnp1033\langfenp1041 {\f0\fs24 \par \par \hich\af0\dbch\af23\loch\f0 Supporting Information \par \par }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 Palladium-Catalyzed Intramolecular }{\b\f3\fs24 \loch\af3\dbch\af23\hich\f3 \'64}{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 -Lactam Formation of Aryl Halides and Amide-Enolates: Syntheses of Cherylline and Latifine \par }{\f0\fs24 \par \par \par \par \hich\af0\dbch\af23\loch\f0 Organic Letters \par \par \par \par }\pard \qj \fi6000\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0\cufi2500 {\f0\fs24 \par \par \par \par \par \par }\pard \qj \fi4800\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0\cufi2000 {\f0\fs24 \hich\af0\dbch\af23\loch\f0 Toshio Honda,* \par \hich\af0\dbch\af23\loch\f0 Hidenori Namiki, \par \hich\af0\dbch\af23\loch\f0 Fumie Satoh \par }\pard\plain \s15\qj \li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0 \i\fs21\lang1033\langfe1041\kerning2\loch\af0\hich\af0\dbch\af23\cgrid\langnp1033\langfenp1041 {\i0\fs24 \par }{\fs24 \par }\pard \s15\qj \fi4800\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0\cufi2000 {\fs24 \hich\af0\dbch\af23\loch\f0 Faculty of Pharmaceutical Sciences, \par \hich\af0\dbch\af23\loch\f0 Hoshi University, \par \hich\af0\dbch\af23\loch\f0 Ebara 2-4-41, \par \hich\af0\dbch\af23\loch\f0 Shinagawa-ku, Tokyo 142-8501, \par \hich\af0\dbch\af23\loch\f0 Japan \par }\pard\plain \qj \li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0 \fs21\lang1033\langfe1041\kerning2\loch\af26\hich\af26\dbch\af23\cgrid\langnp1033\langfenp1041 {\f0\fs24 \par \par \par \par }{\b\f0\fs24 \par \par }\pard \qj \fi241\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0\cufi100 {\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 General Experimental Procedures.}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 IR spectra were recorded as thin films. }{ \f0\fs24\super \hich\af0\dbch\af23\loch\f0 1}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 H NMR and }{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 13}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 C NMR spectra were obtained for a solution in CDCl}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 3 }{\f0\fs24 \hich\af0\dbch\af23\loch\f0 except for cherylline (CD}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 3}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 COCD}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 3}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 ) and latifine (CD}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 3}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 OD), an\hich\af0\dbch\af23\loch\f0 d chemical shifts are reported on the }{\f3\fs24 \loch\af3\dbch\af23\hich\f3 \'64}{ \f0\fs24 \hich\af0\dbch\af23\loch\f0 -scale from TMS as an internal standard. }{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 13}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 C multiplicities were determined with the aid of an APT sequence, separating methylene and quaternary carbons = up, from methyl and methine carbons = down. \par }\pard \qj \li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0 {\f0\fs24 \par }\pard \qj \fi241\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0\cufi100 {\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 5-Benzyloxy-2-br\hich\af0\dbch\af23\loch\f0 omo-4-methoxybenzylamine 6:}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 }{ \f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 A solution of 5-benzyloxy-2-bromo-4-methoxy- benzylalcohol }{\b\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 4}{\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 (6.9 g, 21.5 mmol) and an excess of thionyl chloride (7 mL) in benzene (70 mL) was heated at reflux for 1 h. After evaporation of the solvent and thionyl chloride, th\hich\af0\dbch\af23\loch\f0 e residual chloride }{\b\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 5}{\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 was dissolved into DMF (90 mL). To this solution, was added sodium azide (1.61 g, 24.8 mmol) at room temperature, and the result\hich\af0\dbch\af23\loch\f0 ing solution was stirred at the same temperature for 1h. The mixture was diluted with water and extracted with benzene. The extract was dried (Na}{\f0\fs24\sub\kerning0 \hich\af0\dbch\af23\loch\f0 2}{\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 SO}{ \f0\fs24\sub\kerning0 \hich\af0\dbch\af23\loch\f0 4}{\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 ), and concentrated to leave a crude azide (7.51 g) as a pale yellowish syrup, which, without further pur\hich\af0\dbch\af23\loch\f0 ification, was used in the next step. To a solution of the crude azide (7.51 g) in THF (130 mL) was added triphenylphosphine (5.64 g, 21.5 mmol), and the resulting mixture was stirred for 3 h at ambient temperature. The mixture was treated with water (5 \hich\af0\dbch\af23\loch\f0 \hich\af0\dbch\af23\loch\f0 mL) and then heated at }{\f0\fs24 \hich\af0\dbch\af23\loch\f0 \hich\f0 70\'b0\loch\f0 C for 5 h. Evaporation of the solvent gave a residue, which was purified }{\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 by column chromatography on silica gel with }{\f0\fs24 \hich\af0\dbch\af23\loch\f0 CHCl}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 3}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 / MeOH (15 / 1, v/v) as eluent to afford amine }{ \b\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 6}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (6.15 g, 89%) as colorless solid. IR 3373, 1602 cm}{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 -1}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 ; }{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 1}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 H \hich\af0\dbch\af23\loch\f0 NMR }{\f3\fs24 \loch\af3\dbch\af23\hich\f3 \'64}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 1.70 (2H, br s), 3.77 (2H, s), 3.84 (3H, s), 5.12 (2H, s), 6.94 (1H, s), 7.03 (1H, s), 7.26 \hich\f0 \endash \loch\f0 7.44 (5H, m); }{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 13}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 C NMR }{\f3\fs24 \loch\af3\dbch\af23\hich\f3 \'64}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 up: 46.4, 71.1, 113.7, 134.0, 136.6, 147.5, 149.1; down: 56.2, 114.7, 116.1, 127.3, 127.9, 128.5, 131.9, 132.0; HRMS (EI) Calcd for \hich\af0\dbch\af23\loch\f0 C}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 15}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 H}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 16}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 NO}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 2}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 Br (M}{ \f0\fs24\super \hich\af0\dbch\af23\loch\f0 +}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 ) 321.0364. Found 321.0369. \par }\pard \qj \li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0 {\f0\fs24 \par }\pard \qj \fi241\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0\cufi100 {\b\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 N}{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 -(5-Benzyloxy-2-bromo-4-methoxybenzyl)-(4-benzyloxyphenyl)acetamide 7:}{ \f0\fs24 \hich\af0\dbch\af23\loch\f0 To }{\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 a stirred solution of amine }{\b\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 6}{\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 (681 mg, 2.12 mmol) in Et}{ \f0\fs24\sub\kerning0 \hich\af0\dbch\af23\loch\f0 2}{\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 O (8 mL) was added dropwise a solution of acid chloride (551 mg, 2.12 mmol), prep\hich\af0\dbch\af23\loch\f0 ared from 4-benzyloxyphenylacetic acid and thionyl chloride, in Et}{\f0\fs24\sub\kerning0 \hich\af0\dbch\af23\loch\f0 2}{\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 O (5 mL) at }{\f0\fs24 \hich\af0\dbch\af23\loch\f0 \hich\f0 0\'b0\loch\f0 C }{ \f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 in the usual manner}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 . The reaction mixture was kept alkaline by simultaneous addition of saturated sodium hydrogen carbonate solution. After the stirring had been continued\hich\af0\dbch\af23\loch\f0 for 2 h at the same temperature, the precipitated solid was collected by filtration }{\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 and the filtrate was washed with water and then with Et}{\f0\fs24\sub\kerning0 \hich\af0\dbch\af23\loch\f0 2}{ \f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 O. The solid was recrystallized from MeOH to give amide }{\b\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 7}{\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 (1.0 g, 87%) as thin needles. M.p. 174.5 - 175}{ \f0\fs24 \loch\af0\dbch\af23\hich\f0 \'b0\loch\f0 C. IR 339\hich\af0\dbch\af23\loch\f0 2, 1646, 1610, 1541, 1509 cm}{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 -1}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 ; }{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 1}{ \f0\fs24 \hich\af0\dbch\af23\loch\f0 H NMR }{\f3\fs24 \loch\af3\dbch\af23\hich\f3 \'64}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 3.50 (2H, s), 3.83 (3H, s), 4.34 (2H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 5.9 Hz), 5.01 (2H, s), 5.04 (2H, s), 5.83 (1H, br s), 6.86 (1H, s), 6.93 (2H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 8.7 Hz), 6.98 (1H, s), 7.13 (2H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{ \f0\fs24 \hich\af0\dbch\af23\loch\f0 = 8.7 Hz), 7.28 \hich\f0 \endash \loch\f0 7.43 (10H, m); }{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 13}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 C NMR }{\f3\fs24 \loch\af3\dbch\af23\hich\f3 \'64}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 up: 42.8, 43.4, 70.0, 71.0, 114.0, 126.9, 129.2, 136.5, 136.8, 147.5, 149.5, 158.0, 171.1; down: 56.2, 115.3, 115.4, 115.9, 127.4, 127.5, 127.97, 128.0, 128.6, 130.5; Anal. Calcd for C}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 30}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 H}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 28}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 NO}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 4}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 Br: C, 65.94; H, 5.16; N, 2.50. Found: C, 66.02; H, 5.24; N, 2.\hich\af0\dbch\af23\loch\f0 59. }{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 }{\f0\fs24 \hich\af0\dbch\af23\loch\f0 \par }\pard \qj \fi241\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0 {\f0\fs24 \hich\af0\dbch\af23\loch\f0 \par }\pard \qj \fi240\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0\cufi100 {\f0\fs24 \hich\af0\dbch\af23\loch\f0 }{\b\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 N}{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 -(5-Benzyloxy-2-bromo-4-methoxybenzyl)-}{\b\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 N}{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 -methyl-(4-benzyloxyphenyl)acetamide 8: }{\f0\fs24 \hich\af0\dbch\af23\loch\f0 To a stirred solution of amide }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 7}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (3.23 g, 59.2 mmol) in DMF (60 mL) in the presence of 60% sodium hydride in mineral oil (0.26 g, 65.1 mmol) was added dropwise iodo\hich\af0\dbch\af23\loch\f0 methane (0.57 mL, 71.0 mmol) at ambient temperature and the resulting mixture was stirred for further 2 h at the same temperature. The mixture was treated with saturated NH}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 4}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 Cl solution and extracted with ethyl acetate. The extract was dried (Na}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 2}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 SO}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 4}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 ) and \hich\af0\dbch\af23\loch\f0 concentrated to leave a residue, which was }{\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 purified by column chromatography on silica gel with }{\f0\fs24 \hich\af0\dbch\af23\loch\f0 hexane / EtOAc (3 / 2, v/v) as eluent to give amide }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 8}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (3.08 g, 93%) as colorless needles. M.p. 69.5 \hich\f0 \endash \loch\f0 \hich\f0 70.5\'b0\loch\f0 C. IR 1644, 1609, 1583, 1508 cm}{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 -1}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 ; }{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 1}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 H NMR }{\f3\fs24 \loch\af3\dbch\af23\hich\f3 \'64}{ \f0\fs24 \hich\af0\dbch\af23\loch\f0 2.79 (1.2\hich\af0\dbch\af23\loch\f0 H, s), 2.80 (1.8H, s), 3.53 (0.8H, s), 3.66 (1.2H, s), 3.83 (1.8H, s), 3.86 (1.2H, s), 4.44 (0.8H, s), 4.62 (1.2H, s), 4.93 (2H, s), 4.95 (0.8H, s), 4.97 (1.2H, s), 6.38 \hich\f0 \endash \loch\f0 7.37 (16H, m); HRMS (EI) Calcd for C}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 31}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 H}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 30}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 NO}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 4}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 Br (M }{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 +}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 ) 559.1357. Found 559.1363. Anal.\hich\af0\dbch\af23\loch\f0 Calcd for C}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 31}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 H}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 30}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 NO}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 4}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 Br: C, 66.43; H, 5.40; N, 2.50. Found: C, 66.71; H, 5.43; N, 2.52. \par }\pard \qj \li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0 {\f0\fs24 \par }\pard \qj \fi241\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0\cufi100 {\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 4-(4-Benzyloxyphenyl)-7-benzyloxy-6-methoxy-2-methyl-3-oxo-1,2,3,4-tetrahydroisoquinoline 9:}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 To a stirred solution of Pd(dba)}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 2}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (21 mg, 0.036 mmol), dppe (21 mg, 0.054 m\hich\af0\dbch\af23\loch\f0 mol), and potassium }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 tert}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 -butoxide (60 mg, 0.54 mmol) in dioxane (1.2 mL) was added a solution of amide }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 8}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 \hich\f0 (200 mg, 0.36 mmol) in dioxane (2 mL) at ambient temperature, and the mixture was heated at 100\'b0\loch\f0 C\hich\af0\dbch\af23\loch\f0 for further 1 h. After being }{\f0\fs24 \hich\af0\dbch\af23\loch\f0 c}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 ooled to room temperat\hich\af0\dbch\af23\loch\f0 ure, the mixture was}{\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 partitioned between }{\f0\fs24 \hich\af0\dbch\af23\loch\f0 Et}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 2}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 O and saturated NH}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 4}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 Cl solution, and the aqueous layer was extracted with Et}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 2}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 O. The combined organic layer was dried (Na}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 2}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 SO}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 4}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 ) and concentrated to leave a residue, which was }{\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 purified by col\hich\af0\dbch\af23\loch\f0 umn chromatography on silica gel with }{\f0\fs24 \hich\af0\dbch\af23\loch\f0 hexane / EtOAc (1 / 1, v/v) as eluent to give lactam }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 9}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (139 mg, 81%) as colorless needles. M.p. 122 \hich\f0 \endash \loch\f0 \hich\f0 123\'b0\loch\f0 C. IR 1648, 1608, 1582, 1508 cm}{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 -1}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 ; }{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 1}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 H NMR }{\f3\fs24 \loch\af3\dbch\af23\hich\f3 \'64}{ \f0\fs24 \hich\af0\dbch\af23\loch\f0 3.00 (3H, s), 3.76 (3H, s), 4.13 (1H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 15.7 Hz), 4.50 (1H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 15.7 Hz), 4.98 (2H, s), 5.13 (2H, s), 6.57 (1H, s), 6.72 (1H, s), 6.86 (2H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 8.9 Hz), 7.05 (2H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 8.9 Hz), 7.24 \hich\f0 \endash \loch\f0 7.46 (10H, m); }{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 13}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 C NMR }{\f3\fs24 \loch\af3\dbch\af23\hich\f3 \'64}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 up: 51.9, 69.8, 71.1, 123.0, 128.2, 131.7, 136.7, 136.8, 147.1, 149.4, 157.7, 169.8; down: 34.6, 51.1,\hich\af0\dbch\af23\loch\f0 55.9, 110.6, 111.2, 114.7, 127.1, 127.3, 127.75, 127.79, 128.37, 128.44, 128.8; HRMS (EI) Calcd for C}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 31}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 H}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 29}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 NO}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 4}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (M}{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 +}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 ) 479.2096. Found 479.2106. \par }\pard \qj \fi240\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0\cufi100 {\f0\fs24 \par }\pard \qj \fi241\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0\cufi100 {\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 4-(4-Benzyloxyphenyl)-7-benzyloxy-6-methoxy-2-methyl-1,2,3,4-tetrahydroisoquinoline 10:}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 To a stirred solution of\hich\af0\dbch\af23\loch\f0 lactam }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 9}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (100 mg, 0.21 mmmol) in THF (2 mL) was added 2.0M solution of BH}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 3}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 - SMe}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 2}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 \hich\f0 complex in THF (0.63 mL, 1.25 mmmol) at 0\'b0\loch\f0 C, and the mixture was stirred at room temperature for 2 h. After evaporation of the solvent, the residue was dissolved in dioxane\hich\af0\dbch\af23\loch\f0 :H}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 2}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 O (3:1 v/v, 2 mL), and then treated with K}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 2}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 CO}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 3}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 \hich\f0 (278 mg, 2.09 mmol) at ambient temperature. The resulting mixture was heated at 65\'b0\loch\f0 C for 5 h and cooled to room temperature. The mixture was diluted with brine and extracted with CHCl}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 3}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 . The extract was d\hich\af0\dbch\af23\loch\f0 ried (Na}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 2}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 SO}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 4}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 ) and concentrated to leave a residue, which was }{\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 purified by column chromatography on silica gel with }{\f0\fs24 \hich\af0\dbch\af23\loch\f0 hexane / EtOAc (1 / 2, v/v) as eluent to give amine }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 10}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (88 mg, 91%) as colorless needles. M.p. 144 \hich\f0 \endash \loch\f0 \hich\f0 145\'b0\loch\f0 C. IR 1608, 1582, 1508 cm}{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 -1}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 ; }{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 1}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 H NMR }{\f3\fs24 \loch\af3\dbch\af23\hich\f3 \'64}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 2.37 (3H, s), 2.46 (1H, dd, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 8.8 and 11.1 Hz), 2.94 (1H, dd, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 5.4 and 11.1 Hz), 3.46 (1H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 14.5 Hz), 3.58 (1H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 14.5 Hz), 3.63 (3H, s), 4.14 (1H, dd, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 5.4 and 8.8 \hich\af0\dbch\af23\loch\f0 Hz), 5.01 (2H, s), 5.09 (2H, s), 6.37 (1H, s), 6.57 (1H, s), 6.90 (2H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 8.5 Hz), 7.09 (2H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 8.5 Hz), 7.24 \hich\f0 \endash \loch\f0 7.43 (10H, m); }{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 13}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 C NMR }{\f3\fs24 \loch\af3\dbch\af23\hich\f3 \'64}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 up: 57.9, 61.9, 69.9, 71.0, 129.7, 137.0, 137.2, 146.6, 148.1, 157.3; down: 44.6, 45.8, 55.9, 111.5, 112.5, 114 \hich\af0\dbch\af23\loch\f0 .5, 127.2, 127.4, 127.7, 127.8, 128.39, 128.44, 129.8; HRMS (EI) Calcd for C}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 31}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 H}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 31}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 NO}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 3}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (M}{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 +}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 ) 465.2304. Found 465.2289. These spectroscopic data are identical with those reported.}{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 9}{\f0\fs24 \par }\pard \qj \fi240\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0\cufi100 {\f0\fs24 \par }\pard \qj \fi241\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0\cufi100 {\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 4-(4-Hydroxyphenyl)-7-hydroxy-6-methoxy-2-methyl-1,2,3,4-tetrahydroisoquinoli\hich\af0\dbch\af23\loch\f0 ne (Cherylline) 1:}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 Di-}{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 O}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 -benzylcherylline}{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 10}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 \hich\f0 (70 mg, o.15 mmol) in EtOH (2 mL) was stirred at 60\'b0\loch\f0 C for 24 h under an atmosphere of hydrogen. After the insoluble material was removed by filtration through a pad of Celite, the filtrate was concentrated to lea\hich\af0\dbch\af23\loch\f0 ve a residue, which was }{\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 purified by column chromatography on silica gel with }{\f0\fs24 \hich\af0\dbch\af23\loch\f0 CHCl}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 3}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 / MeOH (10 / 1, v/v) as eluent to give racemic cherylline }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 1}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (31 mg, 68%) as colorless needles. M.p. 217 \hich\f0 \endash \loch\f0 \hich\f0 218\'b0\loch\f0 C. }{ \f0\fs24\super \hich\af0\dbch\af23\loch\f0 }{\f0\fs24 \hich\af0\dbch\af23\loch\f0 The spectroscopic data are identical with those reported.}{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 9}{\f0\fs24 \par }\pard \qj \li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0 {\f0\fs24 \par }\pard \qj \fi241\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0\cufi100 {\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 3-Benzyloxy-2-bromo-4-methoxybenzylamine 12:}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 The amine }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 12}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (3.22 g, 90%) was synthesized from the alcohol }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 11}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (3.57 g, 11.1 mmol) via azide by the same procedure as for the preparation of the amine }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 6}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 , as an oil. IR 3360, 1593, 1485 cm}{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 -1}{ \f0\fs24 \hich\af0\dbch\af23\loch\f0 ; }{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 1}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 H NMR }{\f3\fs24 \loch\af3\dbch\af23\hich\f3 \'64}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 1.57 (2H, \hich\af0\dbch\af23\loch\f0 br s), 3.77 - 3.82 (5H, m), 4.94 (2H, s), 6.77 (1H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 8.3 Hz), 7.00 (2H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 8.3 Hz), 7.17 \hich\f0 \endash \loch\f0 7.50 (5H, m); }{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 13}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 C NMR }{\f3\fs24 \loch\af3\dbch\af23\hich\f3 \'64}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 up: 46.6, 74.5, 119.5, 134.9, 137.1, 145.4, 152.7; down: 56.1, 111.3, 124.1, 128.3, 128.4; HRMS (EI) Calcd for C}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 15}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 H}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 16}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 NO}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 2}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 Br (M}{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 +}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 ) 321\hich\af0\dbch\af23\loch\f0 .0364. Found 321.0362. \par }\pard \qj \fi241\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0 {\f0\fs24 \hich\af0\dbch\af23\loch\f0 \par }\pard \qj \fi240\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0\cufi100 {\f0\fs24 \hich\af0\dbch\af23\loch\f0 }{\b\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 N}{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 -(3-Benzyloxy-2-bromo-4-methoxybenzyl)-(4-benzyloxyphenyl)acetamide 13:}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 The amide }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 13}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (1.86 g, 87%) was synthesized from the amine }{ \b\f0\fs24 \hich\af0\dbch\af23\loch\f0 12}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (1.26 g, 3.92 mmol) and }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 p}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 -benzyloxyphenylacetyl chloride (1.02 g, 3.92 mmol) \hich\af0\dbch\af23\loch\f0 by the same procedure as for the preparation of the amide }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 7}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 , as colorless needles. }{\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 M.p. 150 - 152}{ \f0\fs24 \loch\af0\dbch\af23\hich\f0 \'b0\loch\f0 C (from MeOH). IR 3308, 1649, 1610, 1541, 1509 cm}{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 -1}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 ; }{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 1}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 H NMR }{\f3\fs24 \loch\af3\dbch\af23\hich\f3 \'64}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 3.52 (2H, s), 3.85 (3H, s), 4.40 (2H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 5.9 Hz), 4.99 (2H, s), 5.05 (2H, s), 5.94 (1H, br s\hich\af0\dbch\af23\loch\f0 ), 6.81 (1H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 8.6 Hz), 6.94 (2H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{ \f0\fs24 \hich\af0\dbch\af23\loch\f0 = 8.6 Hz), 7.05 (1H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 8.6 Hz), 7.15 (2H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 8.6 Hz), 7.30 \hich\f0 \endash \loch\f0 7.56 (10H, m); }{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 13}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 C NMR }{\f3\fs24 \loch\af3\dbch\af23\hich\f3 \'64}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 up: 42.8, 43.8, 69.9, 74.5, 119.6, 126.9, 130.1, 136.8, 137.0, 145.3, 153.0, 158.0, 171.1; down: 56.0, 111.1, 115.3, \hich\af0\dbch\af23\loch\f0 125.3, 127.4, 127.9, 128.0, 128.3, 128.4, 128.5, 130.5; HRMS (CI) Calcd for C}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 30}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 H}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 29}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 NO}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 4}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 Br (M}{ \f0\fs24\super \hich\af0\dbch\af23\loch\f0 +}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 +1) 546.1279. Found 546.1266. \par }\pard \qj \li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0 {\f0\fs24 \par }\pard \qj \fi241\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0\cufi100 {\b\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 N}{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 -(3-Benzyloxy-2-bromo-4-methoxybenzyl)-}{\b\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 N}{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 -methyl-(4-benzyloxyphenyl)acetamide 14: }{\f0\fs24 \hich\af0\dbch\af23\loch\f0 The }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 N}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 -methylamide }{ \b\f0\fs24 \hich\af0\dbch\af23\loch\f0 14}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (1.27 g, 77%) was synthesized \hich\af0\dbch\af23\loch\f0 from the amide }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 13}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (1.62 g, 2.97 mmol) by the same procedure as for the preparation of the }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 N}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 -methylamide }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 8}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 , as colorless needles. }{\f0\fs24\kerning0 \hich\af0\dbch\af23\loch\f0 M.p. 28 - 29}{\f0\fs24 \loch\af0\dbch\af23\hich\f0 \'b0\loch\f0 C (from Et}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 2}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 O). IR 1648, 1609, 1584, 1508 cm}{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 -1}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 ; }{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 1}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 H NMR }{\f3\fs24 \loch\af3\dbch\af23\hich\f3 \'64} {\f0\fs24 \hich\af0\dbch\af23\loch\f0 2.90 (1.5H, s), 2.96 (1.5H, s), 3.59 (1H, s), 3.71 (1H, s)\hich\af0\dbch\af23\loch\f0 , 3.81 (1.5H, s), 3.84 (1.5H, s), 4.50 (1H, s), 4.67 (1H, s), 5.00 (2H, s), 5.03 (1H, s), 5.04 (1H, s), 6.68 \hich\f0 \endash \loch\f0 7.56 (16H, m); HRMS (EI) Calcd for C}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 31}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 H}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 31}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 NO}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 4}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 Br (M}{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 +}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 +1) 560.1436. Found 560.1461. \par }\pard \qj \fi240\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0\cufi100 {\f0\fs24 \par }\pard \qj \fi241\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0\cufi100 {\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 4-(4\hich\af0\dbch\af23\loch\f0 -Benzyloxyphenyl)-5-benzyloxy-6-methoxy-2-methyl-3-oxo-1,2,3,4-tetrahydroisoquinoline 15:}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 The lactam }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 15}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (46 mg, 54%) was synthesized from the amide }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 14}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (100 mg, 0.18 mmol) by the same procedure as for the preparation of the lactam }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 9}{ \f0\fs24 \hich\af0\dbch\af23\loch\f0 , as a colorless gum. IR \hich\af0\dbch\af23\loch\f0 1648, 1608, 1584, 1508 cm}{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 -1}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 ; }{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 1}{ \f0\fs24 \hich\af0\dbch\af23\loch\f0 H NMR }{\f3\fs24 \loch\af3\dbch\af23\hich\f3 \'64}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 3.03 (3H, s), 3.88 (3H, s), 4.17 (1H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 15.4 Hz), 4.57 (1H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 10.6 Hz), 4.62 (1H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 15.4 Hz), 4.94 (1H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 10.6 Hz), 5.00 (2H, s), 5.16 (1H, s), 6.83 (2H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 8.7 Hz), 6.91 (1H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 8.4 Hz), 6.\hich\af0\dbch\af23\loch\f0 96 (1H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 8.4 Hz), 7.07 (2H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 8.7 Hz), 7.23 \hich\f0 \endash \loch\f0 7.40 (10H, m); }{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 13}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 C NMR }{\f3\fs24 \loch\af3\dbch\af23\hich\f3 \'64}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 up: 51.9, 69.9, 74.5, 124.6, 130.3, 130.9, 136.9, 137.3, 144.8, 152.0, 157.8, 170.0; down: 34.7, 46.7, 55.8, 111.4, 114.8, 120.6, 127.3, 127.9, 128.0, 128.2, 128.5, 128.6, 12 \hich\af0\dbch\af23\loch\f0 8.8; HRMS (EI) Calcd for C}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 31}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 H}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 29}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 NO}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 4}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (M}{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 +}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 ) 479.2096. Found 479.2124. \par }\pard \qj \li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0 {\f0\fs24 \par }\pard \qj \fi241\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0\cufi100 {\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 4-(4-Benzyloxyphenyl)-5-benzyloxy-6-methoxy-2-methyl-1,2,3,4-tetrahydroisoquinoline 16:}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 The isoquinoline }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 16}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (59 mg, 61%) was synthesized from the lactam }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 15}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (100 mg, 0.21 mmol) by the same \hich\af0\dbch\af23\loch\f0 procedure as for the preparation of the isoquinoline }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 10}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 , as a colorless gum. IR 1608, 1584, 1508 cm}{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 -1}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 ; }{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 1}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 H NMR }{\f3\fs24 \loch\af3\dbch\af23\hich\f3 \'64}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 2.31 (3H, s), 2.63 (1H, dd, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 4.9 and 11.4 Hz), 2.71 (1H, dd, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 3.5 and 11.4 Hz), 3.30 (1H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 14.4 Hz), 3.82 (3H, s), 3.83 (1H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = \hich\af0\dbch\af23\loch\f0 14.4 Hz), 3.93 (1H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 10.5 Hz), 4.25 (1H, dd, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 3.5 and 4.9 Hz), 4.82 (1H, d, }{\i\f0\fs24 \hich\af0\dbch\af23\loch\f0 J}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 = 10.5 Hz), 5.01 (2H, s), 6.82 \hich\f0 \endash \loch\f0 7.29 (6H, m), 7.11 \hich\f0 \endash \loch\f0 7.43 (10H, m); }{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 13}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 C NMR }{\f3\fs24 \loch\af3\dbch\af23\hich\f3 \'64}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 up: 57.9, 61.4, 69.9, 73.3, 131.2, 137.3, 138.1, 139.3, 145.9, 151.1, 156.9; down: 40.4\hich\af0\dbch\af23\loch\f0 , 46.1, 55.8, 111.2, 114.2, 121.4, 127.4, 127.8, 127.9, 128.0, 128.5, 129.4; HRMS (EI) Calcd for C}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 31}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 H}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 31}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 NO}{\f0\fs24\sub \hich\af0\dbch\af23\loch\f0 3}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (M}{ \f0\fs24\super \hich\af0\dbch\af23\loch\f0 +}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 ) 465.2304. Found 465.2289. These spectroscopic data are identical with those reported.}{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 5a}{\f0\fs24 \par }\pard \qj \li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0 {\f0\fs24 \par }\pard \qj \fi241\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0\cufi100 {\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 4-(4-Hydroxyphenyl)-5-hydroxy-6-methoxy-2-methyl-1,2,3\hich\af0\dbch\af23\loch\f0 ,4-tetrahydroisoquinoline (Latifine) 2:}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 Latifine }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 2}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (36 mg, 85%) was synthesized from the benzyl ether }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 16}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 (64 mg, 0.14 mmol) by the same procedure as for the preparation of cherylline }{\b\f0\fs24 \hich\af0\dbch\af23\loch\f0 1}{\f0\fs24 \hich\af0\dbch\af23\loch\f0 , as colorless needles. M.p. 213 \hich\f0 \endash \loch\f0 \hich\f0 215\'b0\loch\f0 C. The spectroscopic data are id\hich\af0\dbch\af23\loch\f0 entical with those reported.}{\f0\fs24\super \hich\af0\dbch\af23\loch\f0 5a}{\f0\fs24 \par }\pard \qj \fi210\li0\ri0\nowidctlpar\aspalpha\aspnum\faauto\adjustright\rin0\lin0\itap0\cufi100 { \par }}