WilliamHill¹Ù·½ÍøÕ¾

±¾ÎĽ«¶Ô°±»ù±£»¤»ùÖеÄÁÚ±½¶þ¼×õ£»ùϵö¾ÙÐмòÒªÏÈÈÝ
¡£

Ò»

¼ò½é

ÁÚ±½¶þ¼×õ£»ù¼°ÆäÑÜÉúÎïÊÇÒ»Àà³£Óõݱ»ù±£»¤»ù£¨½á¹¹¼ûÏÂͼ
£¬ºóÐøͳ³ÆÁÚ±½¶þ¼×õ£»ù
£¬Ïêϸ±£»¤»ùÓÃÆä¼ò³ÆÌåÏÖ£©
£¬ÔÚÖØ´óÓлú·Ö×ÓÓÈÆäÊǶàëĺÍÌÇÀàµÄºÏ³ÉÖÐÓ¦ÓÃÆÕ±é
¡£

ͼ1 ³£¼ûµÄÁÚ±½¶þ¼×õ£±£»¤»ù

ÁÚ±½¶þ¼×õ£»ùͨ³£ÓÃÀ´±£»¤²®°·
£¬ÆäÔÚͨÀýËáÐÔÌõ¼þÏ¡¢´ß»¯Çâ½âÒÔ¼°NH3(l)/Na»¹Ô­µÈϵͳÖоùÄܼá³ÖÎȹÌ
£¬Ïà½ÏÓÚÆäËûõ£»ù±£»¤»ù
£¬ÁÚ±½¶þ¼×õ£»ù¿ÉÒÔʵÏÖ°±»ùµÄÈ«È¡´ú
£¬´Ó¶øÔÚ¶àëĺϳÉÖÐÓÐÓÃÒÖÖÆÏûÐý»¯
¡£È»¶ø
£¬ÆäÔÚ¼îÐÔÌõ¼þºÍÇ¿Ç׺ËÊÔ¼Á±£´æϲ»ÎȹÌ
£¬³£ÓÃË®ºÏëÂÀ´¾ÙÐÐÍѱ£»¤
¡£

¶þ

ÒýÈëÒªÁì

1. ÁÚ±½¶þ¼×Ëáôû·¨

KuritaµÈÈËÔڿǾÛÌÇ°±»ù±£»¤Ê±
£¬½ÓÄÉÁÚ±½¶þ¼×ËáôûÔÚº¬5%Ë®µÄDMFÈÜÒºÖÐ
£¬120¡æ·´Ó¦ÒýÈëPht±£»¤»ù
£¬ÊÕÂÊ>80%
¡£ÔÚ´ËÌõ¼þÏÂ
£¬°±»ù¿ÉÒÔ±»Ñ¡ÔñÐÔ±£»¤
£¬¶øôÇ»ù²»ÊÜÓ°Ï죨õ辶2£©
£¬Í¬Ê±KuritaµÈÈË»¹·¢Ã÷
£¬ÈôÊÇÔÚ´¿µÄDMFÖз´Ó¦
£¬Ôò»á»ñµÃ°±»ùºÍôÇ»ùͬʱ±»±£»¤µÄ¸±²úÆ·£¨õ辶1£©
¡£

´ËÒªÁìͨ³£ÐèÒªÔڽϸߵÄζÈϾÙÐÐ
£¬Èô·Ö×ÓÄÚº¬Óжà¸ö°±»ù£¨ÖÙ°·ºÍ²®°·¹²´æ£©
£¬Ò×±¬·¢ÖÙ°·¼ÓÈëµÄ¸±·´Ó¦
£¬µ«´ËÒªÁìºó´¦Öóͷ£½ÏΪ¼òÆÓ
£¬ÊÊÓÃÓÚ¹¤Òµ»¯Éú²ú
¡£

2. ÁÚ±½¶þ¼×Ëáµ¥ÒÒõ¥·¨

AguilarµÈÈ˽ÓÄÉÁÚ±½¶þ¼×Ëáµ¥ÒÒõ¥ÔڼÈçDIEA£©ºÍËõºÏÊÔ¼ÁPyBOP±£´æÏÂÔö½øõ£°··´Ó¦µÄ±¬·¢
£¬´Ó¶øÒýÈëPht±£»¤»ù
¡£

¸ÃÒªÁì²Ù×÷Ïà¶Ô·±Ëö
£¬·´Ó¦Ê±¼ä½Ï³¤
£¬Í¬Ñù²»ÊÊÓÃÓÚ¶à¸ö°±»ù¹²´æµÄÇéÐÎ
¡£

3. N-ÒÒÑõôÊ»ùÁÚ±½¶þ¼×õ£ÑÇ°··¨

JongheµÈÈËÔÚ¾ÙÐа±»ù±£»¤Ê±
£¬½ÓÄÉN-ÒÒÑõôÊ»ùÁÚ±½¶þ¼×õ£ÑÇ°·ÔÚ¼îÐÔÌõ¼þÏÂÒýÈëPht±£»¤»ù
¡£

¸ÃÒªÁì·´Ó¦ÎÂ˳
£¬±¾Ç®µÍ
£¬¿ÉÒÔÔÚÖÙ°·±£´æµÄÇéÐÎÏÂÑ¡ÔñÐÔ±£»¤²®°·
£¬ÊÇÏÖÔÚ½ÏÁ¿Ö÷Á÷µÄÒ»ÖÖÒýÈëÒªÁì
¡£

4. N-±½»Çõ£»ùÁÚ±½¶þ¼×õ£ÑÇ°··¨

KhalifaµÈÈË¿ª·¢ÁËÒ»ÖÖͨ¹ýN-±½»Çõ£»ùÁÚ±½¶þ¼×õ£ÑÇ°·£¨ÓÉÁÚ±½¶þ¼×õ£ÑÇ°·ºÍ±½»Çõ£ÂÈ·´Ó¦ÖƵ㩸ßЧÒýÈëPht±£»¤»ùµÄÒªÁì
¡£
£¬´ËÒªÁìÔÚÒÒëæ»ØÁ÷µÄÌõ¼þϼ´¿ÉÒýÈëPht
£¬ÊÕÂʸß
£¬ÇÒÎÞÐèÌØÊâ¼Ó¼î
£¬ÊÊÓÃÓÚ¶àÖÖ·¼Ïã°·ºÍÖ¬·¾°·
¡£

Èý

ÍѳýÒªÁì

Ñ¡ÔñºÏÊʵÄÍѳýÒªÁìÖÁ¹ØÖ÷Òª
£¬²»µ«ÍѳýЧÂʸß
£¬»¹ÄÜÈ·±£ÆäËû±£»¤»ù²»ÊÜÓ°Ïì
¡£

1. ë½ⷨ

ͨ³£ÇéÐÎÏÂ
£¬Pht±£»¤»ùµÄÍѳý½ÓÄÉë½ⷨ
£¬Ò»Ñùƽ³£ÔÚË®ºÏëµĴ¼ÈÜÒºÖлØÁ÷·´Ó¦¼´¿ÉÍêÈ«Íѳý
£¬ÔÚ´ËÌõ¼þÏÂ
£¬Cbz¡¢Boc¡¢Ts¡¢TrtµÈ±£»¤»ù²»ÊÜÓ°Ïì
¡£

2. NaBH4/i-PrOH/AcOH·¨

´Ë·¨×÷Ϊë½ⷨµÄÔö²¹
£¬ÔÚë½âЧ¹û²»¼ÑµÄʱ¼ä
£¬½ÓÄÉ´ËÌõ¼þ¿ÉÒԺܺõÄÍÑÈ¥Pht
¡£

3. ÒÒ¶þ°··¨

¸ÃϵÁÐÖеÄËÄÂÈÁÚ±½¶þ¼×õ£»ù£¨TCP£©ÔÚÒÒ¶þ°·µÄ±£´æÏÂÑ¡ÔñÐÔµØÍѳý
£¬¶øõ¥»ùºÍPhtÔò²»ÊÜÓ°Ïì
¡£

ËÄ

ºÏ³ÉÕ½ÂÔ

Pht±£»¤»ù¿ÉÒÔͨ¹ýÔÝʱʧ»îµÄ·½·¨°ü¹ÜÆäËû·´Ó¦µÄÕý³£¾ÙÐÐ
£¬ÔÙÖØС°¸´Éú¡±µÄÕ½ÂÔÓÃÓÚÌض¨³¡¾°
¡£¼øÓÚPhtÔÚ¼îÐÔºÍÇ׺ËÊÔ¼Á±£´æϵÄÎȹÌÐԽϲî
£¬¿ÉÒÔͨ¹ýÓëËÄÇâßÁ¿©·´Ó¦»ñµÃ¸üÎȹ̵ÄÑÜÉúÎï
£¬´ýÆäËû·´Ó¦Íê³Éºó
£¬ÔÙÔÚËáÐÔÌõ¼þÏÂÔÙÉúΪPht»ùÍÅ
£¬¼ÌÐø¼ÓÈëºóÐø·´Ó¦
¡£

±¾ÎĸÅÊöÁË°±»ù±£»¤»ù¡ªÁÚ±½¶þ¼×õ£»ùµÄÒýÈë¡¢ÍѳýÒªÁì¼°ÆäÔںϳÉÕ½ÂÔÖеÄÍØÕ¹Ó¦ÓÃ
£¬Ï£ÍûÄܶÔÏà¹ØÊÂÇéÕßÌṩ²Î¿¼ºÍ˼Ð÷¹¹½¨
¡£

²Î¿¼ÎÄÏ×£º

[1] ¹ùÑÞºÆ
£¬ÝïÇì»Ô
£¬ºÂ˼æµÈ. »¯¹¤²úÆ·Öа±»ùµÄ±£»¤ÓëÍѱ£»¤[J]. ú̿Ó뻯¹¤, 2022, 45, 106-112.

[2] Kurita, K.; lkeda, H.; Harata, M.; et al. Chemoselective Protection of the Amino Groups of Chitosan by Controlled Phthaloylation: Facile Preparation of a Precursor Useful for Chemical Modifications[J]. Biomacromolecules, 2002, 3.

[3] Aguilar, N.; Moyano, A.; Peric¨¤s, M. A.; Riera, A. A General, Catalytic, and Enantioselective Synthesis of (S)-¦Ã-[(S)-1-Aminoalkyl]-¦Ã-lactones[J]. J. Org. Chem. 1998, 63, 3560-3567.
[4] Jonghe, S. D.; Lamote, I.; Herdewijn. P; et, al. Synthesis of Homoceramides, Novel Ceramide Analogues, and Their Lack of Effect on the Growth of Hippocampal Neurons[J]. J. Org. Chem. 2002, 67, 988-996.

[5] Khalifa, A.; Giles, M.; Ali, H. I.; Mohamady, S. Metal- and Catalyst-Free Synthesis of 2-Substituted- Phthalimides Using 2-(Arenesulfonyl)Phthalimide as Key Reagents[J]. Eur. J. Org. Chem. 2023, 26.

[6] Debenham, J. S.; Fraser-Reid, B. Tetrachlorophthaloyl as a Versatile Amine Protecting Group[J]. J.Org.Chem.1996,61,432-433.

[7] Astleford, B.; Weigel, L. O. ¡°SCOPE OF PHTHALIMIDO CHEMISTRY I. EXTENSION OF UTILITY BY CONVERSION TO THE OPCB PROTECTING GROUP.¡±[J]. Tetrahedron Lett., 1991, 32, 3301-3304.