Synthesis of novel phosphorus heterocycles: 2-aryl-1-methyl-2,3-dihydro-1H-2,1-benzazaphosphole 1-oxides

Abstract

combined acidic layers until it was strongly basic. The basic mixture was extracted with CHzClz (5 X 150 mL), and the combined extracts were dried over Na2S04 and concentrated to produce 0.181 g (66%) of a gummy tan solid. Purification by sublimation (90 "C, 2 mm) gave 1 as a waxy white solid; mp 224-227 OC (sealed tube) (lit.4 mp 265-268 "C). Resublimation produced no significant change in melting point. NMR (CDC13) 6 1.5-2.2 (12 H, m), 2.45-2.75 (1 H, br s, exch), 2.90-3.25 (2 H, br s, NCH); M + found, m / e 137.1208 (calcd for C9H15N, m / e 137.1206).N-Methyl-2-azaadamantane-anti-4,8-diol(2b). Treatment of 0.980 g (6.4 mmol) of 12 with CH3NH2 using the reaction conditions for 2a produced 1.06 g (90%) of 2b after recrystallization from acetonitrile: mp 198-201.5 "C; IR (Nujol) 3362 cm-'; NMR (D20 + DCl) 6 (DSS) 4.30 (1 H, m, CHOH), 4.10 (1 H, m, CHOH), 3.43 (2 H, m, CHN), 3.02 (3 H, s, CH,), 1.56-2.40 (8 H, m); M+ found, m / e 183.1258 (calcd for Cl&Il7NO2, m / e 183.1260). N-Ethyl-2-azaadamantane-anti-4,8-diol (2c). Treatment of 0.50 g (3.29 mmol) of 12 with EtNHz using the reaction conditions for 2a produced 0.446 g (69%) of 2c after recrystallization from acetonitrile: mp 178-179 OC; IR (Nujol) 3338 cm-'; NMR (D20) 6 (DSS) 1.01 (3 H, t, CHJ, 1.5-2.6 (8 H, m), 2.75 (4 H, m, NCH), 3.95 (2 H, s, CHOH); M+ found, m / e 197.1414 (calcd for ClIHldO2, m / e 197.1417). N-Isopropyl-2-azaadamantane-an ti-4,8-diol(2d). A solution of 1.00 g (6.58 mmol) of 12 and 1.94 (2.39 mmol) of isopropylamine in 14 mL MeOH was heated at 130 "C in a steel bomb for 24 h. After the solution was cooled, the solvent was evaporated and the residue recrystallized from acetonitrile to produce 0.869 g (63%) of 2 d mp 169-172 "C; IR (Nujol) 3284 cm-'; NMR (DzO + DC1) 6 (DSS) 1.38 (6 H, dd, CH3) 1.6-2.6 (8 H, m), 3.55-4.35 (5 H, m, CHNH, CHOH); M+ found, m / e 211.1567 (calcd for ClzHzlNOz, m / e 211.1573). N-Isoamyl-2-azaadamantane-anti-4,8-diol(2e). Treatment of 1.00 g (6.58 mmol) of 12 with 2.87 g (32.9 "01) of isoamylamine using the reaction conditions for 2d produced 1.058 g (67%) of 2e after recrystallization from acetonitrile: mp 113-116.5 "C; IR (Nujol) 3320 cm-I; NMR (DzO + DCl) 6 (DSS) 0.92 (6 H, d, CHJ, 1.4-2.4 (11 H, m), 3.20-3.67 (4 H, m, CHN), 4.12 (1 H, m, CHOH), 4.28 (1 H, m, CHOH); M+ found, m / e 239.1874 (calcd for C14-H25NO2, m / e 239.1886). N-Benzyl-2-azaadamantane-anti-4,8-diol (2f). Treatment of 1.00 g (6.58 "01) of 12 with 3.52 g (33.0 mmol) freshly distilled benzylamine using the reaction conditions for 2d produced 1.157 g (68%) of 2f after recrystallization from benzene: mp 121-123.5 "C; IR (Nujol) 3440 cm-'; NMR (DzO + DC1) 6 (DSS) 1.75-2.42 (8 H, m, ring CHz, CH), 3.43, 3.49 (2 H, br d, CHN), 4.15 (1 H, m, CHOH), 4.54-4.70 (3 H, m, CHOH, CHzPh), 7.54 (5 H, s, Ph); M+ found m / e 259.1566 (calcd for C16HzlN02, m / e 259.1573). N-Phenyl-2-azaadamantane-anti-4,8-diol(2g). To a stirred solution of 0.400 g (2.63 mmmol) of 12 dissolved in 5 mL of trifluoroethanol under Nz was added 0.270 g (2.89 mmol) of freshly distille...

The Development of Domino Reactions Incorporating the Heck Reaction: The Formation of N‐Heterocycles

“…HPLC was performed with a Grace-Apollo 250 ϫ 10 mm, 5 micron, C18 semipreparative column coupled to a UV detector. The trifluoroacetamide 27 and the benzylamine 28 were prepared by standard literature procedures, [53] except that compound 28 was purified by column chromatography (EtOAc/hexane 1:19). (15) was synthesised by a modification of the procedure of Larock and Zenner.…”

Synthesis of P-Stereogenic Benzoazaphosphole 1-Oxides via Alkynylation of P-Stereogenic ortho-Aurated and ortho-Iodo Phosphinic Amides

“…5, 111.45, 120.6, 124.7 (d, 2 J PC 7.7 Hz), 127.9 (d, 3 J PC 13.1 Hz), 128.1 (d, 3 J PC 11. 5 Hz),130.3,131.0 (d,4 (S)-P-Phenyl-N-((S)-3,3-dimethylbut-2-yl)-P-(…”

“…9 Hz),126.03,126.94,128.11 (d,3 J PC 10.6 Hz), 128.26 (d, 3 J PC 12. 9 Hz),128.29,131.27 (d,4 ( R ) -P -P h e n y l -N -( ( R ) -1 -p h e n y l e t h y l ) -P -( 2 -( ( 2methoxyphenyl)ethynyl)phenyl)-phosphinic Amide (15k). Yield after chromatography (AcOEt/hexane 1:1.5) 95%.…”

“…34−7.69 (m, 11H), 7.76−7.81 (m, 2H), 7.83 (dd, 3 J HH 8. 1 Hz,4 J PH 2.5 Hz, 2H) ppm; 13 C NMR (75.47 MHz, CDCl 3 ): data for major isomer: δ 16.2 (d, 3 J PC 2. 2 Hz),26.6,34.79,59.6,103.9 (d,3 J PC 6.…”

“…Methods available for the preparation of phosphaisoindolin-1-ones (dihydrobenzoazaphosphole 1-oxides) are limited to the ring closure of ( o -chloromethyl)­phenylphosphinic amides 1 (Scheme a) promoted by DBU to give 2 ; nitrene insertion into a benzylic ortho C–H bond through photolysis of phosphinic azides having P -mesityl or P -(2,4,6-triisopropylphenyl) groups 3 to afford heterocycles 4 (Scheme b) and trapping ( R )- N -(1-phenylethyl)­silanamine 5 doubly lithiated at the N and C ortho positions with phenylphosphonic dichloride. The reaction provides ( S P , R C )- 6 in a yield of 43% and high diastereoselectivity (dr > 95:5, Scheme c). , …”