当前位置:首页 >> 能源/化工 >>

有机合成英文文献翻译1


Published on Web 05/24/2007

A Pd(0)-Catalyzed Diamination of Terminal Olefins at Allylic and Homoallylic Carbons via Formal C-H Activation under Solvent-Free Conditions
Haifen

g Du, Weicheng Yuan, Baoguo Zhao, and Yian Shi*
Department of Chemistry, Colorado State UniVersity, Fort Collins, Colorado 80523
Received March 23, 2007; E-mail: yian@lamar.colostate.edu

Diamination of olefins presents an attractive strategy for the synthesis of vicinal diamines, which are contained in various biologically active compounds as important functional moieties and are widely used in asymmetric synthesis as chiral control elements.1 A number of metal-mediated2,3 and -catalyzed diaminations have been developed.4-6 Recently, we reported that conjugated dienes and trienes can be effectively diaminated with high regio- and stereoselectivity using di-tert-butyldiaziridinone (2)7 as nitrogen source and Pd(PPh3)4 as catalyst (Scheme 1).8 Herein we wish to report that terminal olefins can be diaminated at allylic and homoallylic carbons (Scheme 2). Subjecting terminal olefins to the previous diamination conditions [10 mol % of Pd(PPh3)4 in C6D6 at 65 °C] (Scheme 1) gave no diamination products on the olefins. Instead, small amounts of diamination products at allylic and homoallylic carbons were observed. After much experimentation, it was found that this diamination process can be further improved by running the reaction without solvent and by slow addition of di-tert-butyldiaziridinone (2). For example, treating 4-phenyl-1-butene with 5 mol % of Pd(PPh3)4 and 2 (2.75 equiv, added slowly) at 65 °C for 7 h gave a clean diamination product (5a) in 90% yield (Table 1, entry 1). This diamination can be extended to a variety of terminal olefins, including monosubstituted (Table 1, entries 2-6) and 1,1-disubstituted olefins (Table 1, entries 7-11). In all of these cases, the reaction occurred at allylic and homoallylic carbons and essentially only one stereoisomer was obtained.9,10 Diamination product 5 can be deprotected with TFA and concentrated HCl to give a free diamine (an example is shown in Scheme 3). Bisdiamination can also occur for substrates bearing two terminal double bonds. For example, treating 1,9-decadiene with 10 mol % of Pd(PPh3)4 and 2 for 12 h led to the formation of a mixture (meso/ DL) of bisdiamination products 8a and 8b in 61% yield (Scheme 4). X-ray structure of 8a is shown in Figure 1. It appears that the first diamination has little effect on the stereochemistry of the second diamination. However, when the reaction was carried out with 1,7-octadiene, bisdiamination product 11 was obtained as a single diastereomer in 47% yield (Scheme 5), suggesting that the first diamination influences the stereochemical outcome of the second diamination. The stereochemistry of 11 was determined by X-ray structure (Figure 1). When the reaction was carried out with 5 mol % of Pd(PPh3)4 at 65 °C for 12 h, substantial amounts of compounds 10a (14% yield) and 10b (20% yield) were isolated. When isolated compounds 10a and 10b were subjected to the diamination conditions, both compounds were converted to compound 11, suggesting that 10a and 10b are possible reaction intermediates toward 11. While a precise reaction mechanism awaits further study, a plausible catalytic cycle is shown in Scheme 6. The Pd(0) first inserts into the N-N bond of diaziridinone 2 to form a fourmembered Pd(II) species (12),11 which complexes with olefin 4 to form 13. Upon removing an allylic hydrogen, complex 13 forms π-allyl Pd complex 14,12,13 which gives diene 15 and regenerates
7496
9

Scheme 1

Scheme 2

Table 1. Catalytic Diamination of Terminal Olefinsa

a All reactions were carried out with olefin (1.6 mmol), Pd(PPh ) (0.08 3 4 mmol), and di-tert-butyldiaziridinone (4.4 mmol) (added by syringe pump at 0.4 mmol/h) at 65 °C under argon unless otherwise stated. b Di-tertbutyldiaziridinone (4.4 mmol) was added by syringe pump at 0.8 mmol/h. c These products are acid sensitive and were purified on less acidic silica gel (Iatrobeads 6RS-8060, Mitsubishi Kagaku Iatron, Inc., Japan). d Isolated yield based on the olefin.

the Pd(0) catalyst after -H elimination.14 Subsequently, diene 15 complexes with 12 to form 17, which is then converted into π-allyl
10.1021/ja072080d CCC: $37.00 ? 2007 American Chemical Society

J. AM. CHEM. SOC. 2007, 129, 7496-7497

COMMUNICATIONS

activation16 using di-tert-butyldiaziridinone (2) as nitrogen source and Pd(PPh3)4 as catalyst, giving the diamination products in good yields with high stereoselectivity. Bisdiamination can also be achieved for substrates bearing two terminal double bonds. This diamination uses readily available terminal olefins and is complementary to the previous diamination process of conjugated dienes. Further efforts will be devoted to studies of the reaction mechanism, search for a more effective catalytic process with different nitrogen sources and metal catalysts, and expansion of the substrate scope as well as the asymmetric process.
Figure 1. The X-ray structures of compounds 8a and 11. Scheme 3

Acknowledgment. We are grateful for the generous financial support from the Camille and Henry Dreyfus Foundation and the Monfort Foundation (CSU).
Supporting Information Available: Diamination procedures, deprotection procedure, characterization and NMR spectra of 5, 6, 8a,b, 10a,b, and 11, and the X-ray data of 8a, 8b, and 11. This material is available free of charge via the Internet at http://pubs.acs.org.

Scheme 4

References
(1) For leading reviews, see: (a) Lucet, D.; Gall, T. L.; Mioskowski, C. Angew. Chem., Int. Ed. 1998, 37, 2580. (b) Mortensen, M. S.; O’Doherty, G. A. Chemtracts: Org. Chem. 2005, 18, 555. (c) Kotti, S. R. S. S.; Timmons, C.; Li, G. Chem. Biol. Drug Des. 2006, 67, 101. (2) For examples of metal-mediated diaminations, see the following. Co: (a) Becker, P. N.; White, M. A.; Bergman, R. G. J. Am. Chem. Soc. 1980, 102, 5676. Hg: (b) Barluenga, J.; Alonso-Cires, L.; Asensio, G. Synthesis 1979, 962. Mn: (c) Fristad, W. E.; Brandvold, T. A.; Peterson, J. R.; Thompson, S. R. J. Org. Chem. 1985, 50, 3647. Os: (d) Chong, A. O.; Oshima, K.; Sharpless, K. B. J. Am. Chem. Soc. 1977, 99, 3420. (e) Muniz, ? K.; Nieger, M. Synlett 2003, 211. (f) Muniz, K.; Nieger, M. Chem. ? Commun. 2005, 2729. Pd: (g) Backvall, J.-E. Tetrahedron Lett. 1978, ¨ 163. Tl: (h) Aranda, V. G.; Barluenga, J.; Aznar, F. Synthesis 1974, 504. (3) For a recent Cu(II)-mediated intramolecular diamination, see: Zabawa, T. P.; Kasi, D.; Chemler, S. R. J. Am. Chem. Soc. 2005, 127, 11250. (4) For Rh(II)- and Fe(III)-catalyzed diamination with TsNCl2, see: (a) Li, G.; Wei, H-X.; Kim, S. H.; Carducci, M. D. Angew. Chem., Int. Ed. 2001, 40, 4277. (b) Wei, H-X.; Kim, S. H.; Li, G. J. Org. Chem. 2002, 67, 4777. (5) For a recent Pd(II)-catalyzed intermolecular diamination of conjugated dienes, see: Bar, G. L. J.; Lloyd-Jones, G. C.; Booker-Milbun, K. I. J. Am. Chem. Soc. 2005, 127, 7308. (6) For a recent Pd(II)-catalyzed intramolecular diamination of terminal olefins, see: Streuff, J.; Hovelmann, C. H.; Nieger, M.; Muniz, K. J. Am. Chem. ¨ ? Soc. 2005, 127, 14586. (7) Prepared based on the reported method: Greene, F. D.; Stowell, J. C.; Bergmark, W. R. J. Org. Chem. 1969, 34, 2254. (8) Du, H.; Zhao, B.; Shi, Y. J. Am. Chem. Soc. 2007, 129, 762. (9) Other isomers were barely detectable by 1H NMR of the crude reaction mixture if there was any. (10) No reactions were observed for olefins with internal double bonds such as trans-5-decene and cis-cyclooctene under current conditions. (11) Komatsu, M.; Tamabuchi, S.; Minakata, S.; Ohshiro, Y. Heterocycles 1999, 50, 67. (12) For leading reviews on generation of π-allyl Pd complexes from olefins with PdX2, see: (a) Trost, B. M. Acc. Chem. Res. 1980, 13, 385. (b) ?kermark, B.; Zetterberg, K. In Handbook of Organopalladium Chemistry for Organic Synthesis; Negishi, E.-i., Ed.; John Wiley & Sons: New York, 2002; p 1875. (13) For a recent book, see: Tsuji, J. Palladium Reagents and Catalysts: New PerspectiVe for the 21st Century; John Wiley & Sons: New York, 2004. (14) For leading reviews on formation of dienes from π-allyl Pd complexes, see: (a) Ref 12a. (b) Shimizu, I. In Handbook of Organopalladium Chemistry for Organic Synthesis; Negishi, E.-i., Ed.; John Wiley & Sons: New York, 2002; p 1981. (15) For leading references on cis-aminopalladation, see: (a) Isomura, K.; Okada, N.; Saruwatari, M.; Yamasaki, H.; Taniguchi, H. Chem. Lett. 1985, 385. (b) Ney, J. E.; Wolfe, J. P. Angew. Chem., Int. Ed. 2004, 43, 3605. (c) Brice, J. L.; Harang, J. E.; Timokhin, V. I.; Anastasi, N. R.; Stahl, S. S. J. Am. Chem. Soc. 2005, 127, 2868. (d) Liu, G.; Stahl, S. S. J. Am. Chem. Soc. 2006, 128, 7179. (16) For a recent leading review on metal-catalyzed oxidative C-H functionalization, see: Dick, A. R.; Sanford, M. S. Tetrahedron 2006, 62, 2439.

Scheme 5

Scheme 6. A Proposed Catalytic Cycle for Diamination

Pd complex 18 after migratory insertion.8,15 Finally, 18 undergoes reductive elimination to form product 5 and regenerate the Pd(0) catalyst. In summary, a variety of terminal olefins have been effectively diaminated at allylic and homoallylic carbons via formal C-H

JA072080D

J. AM. CHEM. SOC.

9

VOL. 129, NO. 24, 2007 7497

形 物合复,后氢丙烯个一除移在, 物产 可个一但,究研步一进待有理机应反的切确然虽 变 。体间中应反的 为 成形合配 烃烯与 , (物产的)Ⅱ(钯 ) 状环元四个一成形键 的 物产化胺二 是能可 和 转都物合化 入插先首钯价零。示所 图如环循化催的信 转两这,下件条应明表,二物合化成换物合化的到 种 反化胺 在 和 。定决类种烃烯由率产离分 。)本日,司 得离分当。) 率产( 和) 率产( 物合 公学化菱三 号型,器波示位电影 投(化纯胶硅性酸量少用,感敏酸对品产些这。加添 化的量大到得离分,时小 应反℃ 在 的 以泵射注用) (酮丙环杂氮二基 度浓量用当。) 形图如(定确线射 由构结学化 丁叔二代氮 。明说有另非除,应反下护保气氩℃ 在)加添时小 尔摩毫 以泵射注用() ( 体立的 物产。型构学化体立的物产化胺二二第响 酮丙环杂氮二基丁叔二代氮,)尔摩毫 ( 影物产化胺二一第明表这。) 图如( 率产, ,) (烃烯用使应反的有所 物产化胺二体映对非的一单到得应反行进烯二辛 用当而然,大不响影型构学化体立的物产化胺二 的生产步二第对物产化胺二的生产步一第示显它, 形图如构结线射 的 ) 图如( 率产, 和 ) 旋消内( 合混的化胺二双成形时小 应反 和 物 , 的 度浓量和烯二癸 , 用如例 上质物 的键双端末有含链基在生发可也应反化胺二双 ) 图如( 胺二的离游到得而护保脱酸盐浓和酸乙氟 。 三用以可 物产化胺二 体构异体立个一到得只上 。 本基且上碳位丙烯高和基丙烯在生发应反,下况情 些这有所在。) 目项, 表(烃烯代取二 和 ) 目项, 表(代取单括包,烃烯端末种各到广 推以可应反化胺二种这。) 目项, 表( 率产 ) ) ( 产化胺二的纯到得时小 应反℃ 在 入加慢 物 缓,量当 ( 和 的 度浓量质物和烯 丁 基苯 用,如例。善完步一进下件条剂溶无在 ) (酮丙环杂氮二基丁叔二代氮入加慢缓过通以可 程过化胺二这现发才,后验实次多在。物产化胺二 的碳丙烯高和丙烯在量少到察观却反相,烃烯的化 胺二有没到得下 案方 ℃ 中苯代氘在 的 度浓量 件条化胺二的前先在烃烯端末使 。) 图如(成合化胺二行进碳位等和基丙 烯在以可烃烯端末道报望希们我此在。 ) 图如( 成合化胺二行进下性择选体立高在的效有剂化催作 以源氮为作 ) (酮丙环杂氮二基丁叔二 代氮用以可烯三、烯二轭共了道报们我,近最。 发开已应反成合质物类胺二的化催和 导介属金干 若。 件元学化性手成合称对不在用应泛广并成合团 基能功要重的物合化性活物生种各含包中其,法方 的胺二邻成合的地效有个一了供提烃烯类胺二 ude.etatsoloc.ramal@naiy :liam-E ;稿收日 32 月 3 年 7002 在,32508 市堡斯林柯州多拉罗科,系学化学大立州多拉罗科国美 安一史、国保赵、成伟袁、峰海杜 成合化胺二的碳基丙烯高及基丙烯的烃烯端末的化活 H-C 化催钯下件条剂溶无在 成合化胺二的碳基丙烯高及基丙烯的烃烯端末的化活 H-C 化催钯下件条剂溶无在 成合化胺二的碳基丙烯高及基丙烯的烃烯端末的化活 H-C 化催钯下件条剂溶无在 成合化胺二的碳基丙烯高及基丙烯的烃烯端末的化活 H-C 化催钯下件条剂溶无在 志杂会学学化国美 志杂会学学化国美 :文译 :文译 志杂会学学化国美 志杂会学学化国美 :文译 :文译
11 8a 1 Pd(PPh3)4
4-6

X Pd-(PPh3)4 65 10a 14% 10a 10b

2

1,1 -

11

5% Pd-(PPh3)4 65 7 90% 1 1

8b

1

12

47%

8

2,3

61%

1 9-

5

65

11 1

12 10b

2

9,10

](

4 8a X

7

7-11

1

1)

10a 10b 20% 42 2.75 [ 1 2

10% Pd(PPh3)4 /DL ,

5

Pd-(PPh3)4

11

10%

-1-

2-6

1

5a ,

5%

1,7

2

3

Table 1. Catalytic Diamination of Terminal Olefinsa

Scheme 2

Scheme 1

0.08 4.4 mmol 65

13

a

c

6 2 N-N 12
d

4.4 mmol

Iatrobeads 6RS-8060

11

0.4

1.6 mmol

/

4

b

0.8 mmol/h

Pd-(PPh3)4

13

和位丙烯在地效有经已烃烯端末种各,之总 。剂化催钯价零生再和 品产成形除消原还过经 物合配,后最 。 物合配钯基丙烯 成换转后入 插移迁钯在 物合化, 物合化成合配 与 烯 二,后随 。钯价零生再和 品产成形除消原还过经 物合配,后最 。 物合配钯基丙烯 成换转 后入插移迁钯在 物合化 物合化成合配 与 , 烯二,后随 。钯价零剂化催的生再和 烯二生产后 除消在 物合配 , 物合配钯基丙烯 成
18 15

:献文考参 : )略译翻( 献文考参 :献文考参

。看查上gro.sca.sbup//:ptth 在网联互过通费免以可料材 些这,据数线射- X的11和 ,b8 ,a8及以谱光 振共磁核和征表的11 和 ,b,a01,b,a8 ,6 ,5 ,骤步护保脱,骤步成合化胺二:息信持支 谢感 示表持支政财慨慷的)USC(会金基特福蒙和 : 会金基斯福雷德利亨与尔米卡对们我 谢鸣 。程过成合称对不于用并围范链基 物底的用适应反大扩,程过化催的效有更的 剂化催属金和源氮同不用采求寻,究研的理 机应反于力致将力努步一进。充补相互程过 应反 化胺 二的 烃烯 二轭 共前之 和并 烃烯 端 末的成现用使应反化胺二个这。现实上物合 化的 键双 端末 个两 有含 链基在 以可 也化 胺 二双。性择选体立高较有且品产化胺二的率 产好良到得,剂化催为作 以源氮 为作) (酮丙环杂氮二基丁叔二代氮以应 反 成合化胺二行进化活 过通碳位等
Pd-(PPh3)4 C-H 2
16

π-

15

12

π-

12

π15

14 12,13

17

5

17

5

18

18

8,15

17

8,15

17

14

14

14

β -H

18


相关文章:
有机合成英文文献翻译1
有机合成英文文献翻译1_理学_高等教育_教育专区。有机合成英文文献翻译1译文: 译文: 美国化学学会杂志 无溶剂条件下钯催化 活化的末端烯烃 烯丙基及高烯丙基 端...
有机合成英文文献翻译2
有机合成英文文献翻译2_理学_高等教育_教育专区。有机合成英文文献翻译2 ...Wipf审核。 1.步骤 1.步骤特戊酰氯合成:将一升的三颈圆底烧瓶配备一个有...
Analysis of recycled poly (styrene-co-butadiene)有机合成英文文献翻译
a new approach in solid catalysts for biodiesel production 翻译 回收的聚(苯...Garnica1*, Mario Paredes-Casillas1, Tito E Herrera-Larrasilla1, Felicia ...
有机合成英语论文原文与翻译[1]
有机合成英文文献翻译2 6页 2下载券 有机合成经验总结-08030... 22页 免费...1.步骤 1.步骤注意:所有操作必须在一个有效的通风橱中进行,因为异氰类物质有...
【有机合成英语论文原文与翻译】
关键词:专业英语 1/2 相关文档推荐 有机合成英语论文原文与翻... 6页 5财富...英语论文翻译 10页 免费如要投诉违规内容,请到百度文库投诉中心;如要提出功能问题...
英文文献1翻译
英文文献1翻译_英语学习_外语学习_教育专区。河北工程大学学位论文 有机食品市场...LY,卡波什瓦大学,动物科学学院,经济和组织 协会 1 河北工程大学学位论文 第一...
有机合成双语段落翻译一
有机合成双语 20 段翻译 1---页码 6 The relationship between functional groups may provide the clue to a particular strategy (e.g. a β -hydroxy...
英文文献翻译李晶莹1
英文文献翻译李晶莹1_物理_自然科学_专业资料。猴头菇多糖对树突状细胞的免疫调节作用摘要 :猴头菌属多糖已被证明具有免疫调节活性。我们发现的生物活性成分由 20%的...
英文文献翻译1-6
英文文献翻译1-6_英语学习_外语学习_教育专区。2. RELATIONSHIPS AMONG SOURCE ...本文引入种族因素,白人感知负面口碑比正面口碑更有影响力;黑人态 度受种族内群体...
英文文献1翻译
英文文献翻译1 5页 1下载券 有机合成英文文献翻译1 4页 2下载券 车牌识别英文...《创意产业专题报告》 , 当年英国创意产业的产值大约 为 1 125 亿英镑, 相当...
更多相关标签:
有机合成文献 | 英文文献翻译网站 | 参考文献翻译成英文 | 中文文献翻译成英文 | 英文文献翻译 | 英文文献翻译软件 | 翻译英文文献的软件 | 翻译英文文献算抄袭吗 |