鍫垮挤(qi谩ng)搴﹁秴閬�(gu貌)寮�(qi谩ng)鍫�(pKa>26)鐨勫牽鍗宠绋辩偤瓒呭挤(qi谩ng)鍫�(super basie)銆傚湪鏈夋(j墨)鍙嶆噳(y墨ng)涓�锛岃秴寮�(qi谩ng)鍫垮彲灏囩⒊-姘嵉鍘婚櫎璩�(zh矛)瀛愶紝浣跨景鍩哄け鍘�α-姘畩鎴愮儻閱囧紡绲�(ji茅)妲�(g貌u)鎴栧オ鍙栧寲鍚堢墿涓殑娲绘綉姘�锛屽緸鑰屾湁鍔╀簬鍙嶆噳(y墨ng)鐨勯爢鍒╅��(j矛n)琛�銆傚父鐢ㄨ秴寮�(qi谩ng)鍫夸富瑕佸寘鎷兒鍩洪噾灞寲鍚堢墿銆佺兎鍩洪噾灞嫲鍖栧悎鐗�銆侀唶鐨勫牽閲戝爆楣藉強鐒�(w煤)姗�(j墨)楣芥矮鍖栫墿绛�锛屽畠鍊戣寤ｆ硾鎳�(y墨ng)鐢ㄤ簬閱�(y墨)钘�銆佽静(n贸ng)钘�銆佸寲宸ョ瓑鏈夋(j墨)鍚堟垚涓殑鍌寲銆佺府鍚�銆侀噸鎺掑拰闁�(k膩i)鐠�(hu谩n)绛夊弽鎳�(y墨ng)涓�銆�
鐧鹃潏濞佽秴寮�(qi谩ng)鍫跨郴鍒楃敘(ch菐n)鍝佸叿鏈変互涓嬬壒榛�(di菐n)锛氭椿鎬у牽鍚噺楂橈紝鍙嶆噳(y墨ng)鏀剁巼楂�锛涘寘瑁濈簿鑹�锛屽ぇ閮ㄥ垎鐐哄彲鎶藉彇寮忕幓鐠冪摱锛屽濂楀畨鍏ㄩ惖妗跺寘瑁�锛屽彲鏈夋晥寤堕暦(zh菐ng)鐢�(ch菐n)鍝佸瓨鍎�(ch菙)鏅�(sh铆)闁擄紱鍦�(gu贸)鍏�(n猫i)鐝�(xi脿n)璨ㄧ敘(ch菐n)鍝佸厖瓒�锛屽苟寰炲厠绱�(j铆)鑷冲叕鏂ょ礆(j铆)绌�(w臎n)瀹氫緵鎳�(y墨ng)锛涙澶�锛岀櫨闈堝▉閭勬彁渚涘畾鍒跺寘瑁濇湇鍕�(w霉)锛屽彲鎸夌敤鎴舵墍闇�閫�(j矛n)琛屽皥灞倷璨ㄩ�佽波锛屼互纰轰繚鐢ㄦ埗鐨勭鐮斿(sh铆)椹�(y脿n)鍜屽伐妤�(y猫)鐢熺敘(ch菐n)鐨勯爢鍒╅��(j矛n)琛�銆�
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鈻� 鐢�(ch菐n)鍝佸垪琛�
|
椤炲垾
|
CAS
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绲�(ji茅)妲�(g貌u)寮�
|
涓枃鍚嶇ū
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瑕�(gu墨)鏍�
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鐢�(ch菐n)鍝佺法铏�(h脿o)
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鐑峰熀閲戝爆鍖栧悎鐗�
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鍏敳鍩轰簩纭呭熀鑳�鍩洪墍
KHMDS, KMDS
|
1M in THF
|
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鍏敳鍩轰簩纭呭熀鑳哄熀閳�
NaHMDS, NaMDS
|
2M in THF
|
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鍏敳鍩轰簩纭呭熀鑳哄熀閶�
LiHMDS, LHMDS
|
1M in THF
|
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浜岀暟涓欏熀鑳哄熀閶�
LDA
|
2M in THF/n-heptane ethylbenzene
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姝ｄ竵鍩洪嫲
n-BuLi
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1.6M in hexanes
|
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2.4M in hexanes
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鍙斾竵鍩洪嫲
t-BuLi
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1.6M in pentane
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浠蹭竵鍩洪嫲
s-BuLi
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1.4M in cyclohexane/hexane
|
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閱囩殑鍫块噾灞菇
|
|
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鐢查唶閳�
CH3ONa
|
anhydrous powder
|
|
|
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涔欓唶閴�
C2H5OK
|
95%
|
|
|
|
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鍙斾竵閱囬墍
t-BuOK
|
1M in THF
|
|
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99%
|
|
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鍙斾竵閱囬垑
t-BuONa
|
99%
|
|
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鐒�(w煤)姗�(j墨)楣芥矮鍖栫墿
|
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NaH
|
姘寲閳�
NaH
|
60% dispersion in mineral oil
|
|
|
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LiH
|
姘寲閶�
LiH
|
95%
|
|
|
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KH
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姘寲閴�
KH
|
25 to 35 wt.%, dispersion in mineral oil
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鈻� 鎳�(y墨ng)鐢ㄤ粙绱�
1. 鑳哄熀閲戝爆鍖栧悎鐗�
鑳哄熀閲戝爆鍖栧悎鐗╋紙濡侼aHMDS銆並HMDS绛夛級鍧囩偤闈炶Κ鏍告�ц秴寮�(qi谩ng)鍫�锛屼富瑕佺敤浜庤劔鍘绘湁姗�(j墨)鍖栧悎鐗╃殑娲绘�ф矮锛屾噳(y墨ng)鐢ㄤ簬褰㈡垚鐑唶鐨勫弽鎳�(y墨ng)銆佺儻閱囬叝绔嬮珨灏堜竴鍏嬭悐妫噸鎺掑弽鎳�(y墨ng)銆佸皣閱涜綁(zhu菐n)鍖栫偤纭呬簽鑳虹殑鍙嶆噳(y墨ng)銆佺敓鎴愮府姘寸敇娌归吀閰殑鍙嶆噳(y墨ng)銆�β-鍏�(n猫i)閰拌兒鐨勫弽鎳�(y墨ng)銆佽姵鍩虹兎鍩洪啔閬告搰鎬ф柗瑁傚弽鎳�(y墨ng)绛�锛屾サ鏄撳皣鍙儻閱囧寲鐨勯叜绛夌祼(ji茅)妲�(g貌u)瀹氶噺鍦拌綁(zhu菐n)璁�?y艒u)姗勨攼闄呮祰Y(ji茅)妲�(g貌u)锛屼究浜庡悎鎴愩��
濡傦細
Roos 绛変互β-姘ㄥ熀閱囩偤搴曠墿缍�(j墨ng)閬�(gu貌)涓夋鍙嶆噳(y墨ng)寰楀埌鍏�(n猫i)閰�锛屾鍏�(n猫i)閰湪 NaHMDS浣滅敤涓嬭垏Br(CH2)4OTf (Bromotriflate) 鐧�(f膩)鐢熷彇浠ｅ弽鎳�(y墨ng)鐢熸垚婧寸兎鍩哄収(n猫i)閰� [1]锛�
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β-鍏�(n猫i)閰拌兒鍖栧悎鐗╁湪NaHMDS浣滅敤涓嬮��(j矛n)琛岄唶瑙ｇ敓鎴愭姉鐧岃棩鐗╃传鏉夐唶閲嶈涓枔楂擺2]锛�
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2. 鐑峰熀閲戝爆閶板寲鍚堢墿
鐑峰熀閲戝爆閶版牴鎿�(j霉)鍙嶆噳(y墨ng)鐗╃殑涓嶅悓锛岄櫎浣滅偤寮�(qi谩ng)鍫挎�ц│鍔戝锛屼篃鍙綔鐐哄挤(qi谩ng)瑕牳鍔戣垏閭勫師鍔戯紝鍏跺弽鎳�(y墨ng)鎬ц兘姣斾竴鑸牸姘忚│鍔戣寤ｆ硾鑰屼笖澶氭ǎ鍖�銆備綔鐐轰竴绋挤(qi谩ng)鍫夸娇鐢ㄦ檪(sh铆)锛岃兘灏囪ū澶氱ó纰�-姘嵉鍘婚櫎璩�(zh矛)瀛愶紙閲戝爆鍖栧弽鎳�(y墨ng)锛�锛岃兘灏囪ū澶氬急甯冩湕鏂壒閰稿幓闄よ唱(zh矛)瀛�锛屾搮闀�(zh菐ng)鍘婚櫎闆欓嵉纰充笂鐨勯沟褰㈡垚璨�(f霉)闆㈠瓙锛涗綔鐐鸿Κ鏍告�ц│鍔戞檪(sh铆)鏄父鐢ㄧ殑鐑峰熀鍖栬│鍔戙�備緥濡�锛屽湪鑳哄熀鑸囩⒊閰镐簩鐢查叝鐨勫姞鎴愬弽鎳�(y墨ng)涓�锛岄噰鐢ㄦ涓佸熀閶扮偤鍫匡紝姝ｄ竵鍩洪嫲鎵紨灏囪兒鍘婚櫎璩�(zh矛)瀛愮殑瑙掕壊[3] 锛�
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姝ゅ锛屽彲鐩存帴閫�(j矛n)琛岄噾灞寲鍙嶆噳(y墨ng)锛岃垏鐑翠綔鐢紝鐢熸垚鐨勭兎鍩洪嫲鍙垏澶氱ó鐗╄唱(zh矛)鐧�(f膩)鐢熷弽鎳�(y墨ng)?锛熺爞l(f膩)鐢熼沟绱�-閶颁氦鎻涘弽鎳�(y墨ng)锛涘彲鑸囬啗銆侀叜鐧�(f膩)鐢熻Κ鏍稿姞鎴愬拰鍙栦唬鍙嶆噳(y墨ng)锛岀敓鎴愪徊閱囨垨鍙旈唶锛涗篃鍙互鍦ㄧ儻鐑撮洐閸典笂鐧�(f膩)鐢熷姞鎴愮瓑锛�
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3.鍫块噾灞菇椤�
閱囩殑鍫块噾灞菇鐢ㄤ綔寮�(qi谩ng)鍫挎�ц│鍔戝彲鍙冭垏寰堝鍙嶆噳(y墨ng)锛屽缇ラ啗鍙嶆噳(y墨ng)銆佸厠钀婃．绺悎鍙嶆噳(y墨ng)銆丠orner-Wadsworth-Emmons鍙嶆噳(y墨ng)绛�銆傚弽鎳�(y墨ng)涓紝寮�(qi谩ng)鍫胯│鍔戞彁渚涘挤(qi谩ng)鍫挎�х兎姘у熀璨�(f霉)闆㈠瓙RO-锛屽オ鍙栧寲鍚堢墿涓殑娲绘綉姘紝寤ｆ硾鎳�(y墨ng)鐢ㄤ簬绺悎銆侀噸鎺�銆侀枊(k膩i)鐠�(hu谩n)绛夊弽鎳�(y墨ng)涓��
4.鐒�(w煤)姗�(j墨)楣芥矮鍖栫墿
鐒�(w煤)姗�(j墨)楣芥矮鍖栫墿鍦ㄦ湁姗�(j墨)鍚堟垚涓敤閫旈潪甯稿唬娉�锛屾渶甯哥敤浜�1,3-浜岀景鍩哄寲鍚堢墿鎴栭浼肩墿鐨勫幓璩�(zh矛)瀛愬寲鍙嶆噳(y墨ng)锛岀敓鎴愮浉鎳�(y墨ng)鐨勫彲浠ヨ鐑峰熀鍖栭噾灞寲鍚堢墿锛屽緸鑰岃兘鐢熸垚鍚勭ó鍚勬ǎ鐨勬湁姗�(j墨)鍖栧悎鐗�銆傚父瑕�(ji脿n)鍙嶆噳(y墨ng)濡傦細Dieckmann绺悎鍙嶆噳(y墨ng)銆丼tobbe绺悎鍙嶆噳(y墨ng)銆丏arzens绺悎鍙嶆噳(y墨ng)鍜孋laisen绺悎鍙嶆噳(y墨ng)绛�銆�
Ref.
[ 1 ] G H P Roos, K A Dastlik. Synth. Commun., 2000, 33:2197~2208.
[ 2 ] 鍖栧(xu茅)宸ユキ(y猫)鑸囧伐绋�.2001,18(5):285-288.
[ 3 ] Journal of Organometallic Chemistry, 1996, 512:219-224.