274:
241:
103:
201:, the alkene inserts into either the metal-acyl or the metal-hydride bonds. In the final step, the resulting alkyl-acyl or beta-ketoalkyl-hydride complex undergoes
428:
Catalytic decarbonylation, hydroacylation, and resolution of racemic pent-4-enals using chiral bis(di-tertiary-phosphine) complexes of rhodium(I)
197:. The resulting acyl hydride complex next binds the alkene. The sequence of oxidative addition and alkene coordination is often unclear. Via
480:
Asymmetric cyclization reactions. Cyclization of substituted 4-pentenals into cyclopentanone derivatives by rhodium(I) with chiral ligands
273:
256:
was demonstrated in the form of a kinetic resolution. A true asymmetric synthesis was also described. Both conversions employed
240:
205:. A competing side-reaction is decarbonylation of the aldehyde. This process also proceeds via the intermediacy of the acyl
349:
K. Sakai; J. Ide; O. Oda; N. Nakamura (1972). "Synthetic studies on prostanoids 1 synthesis of methyl 9-oxoprostanoate".
509:
Synthesis of D- and L-Carbocyclic
Nucleosides via Rhodium-Catalyzed Asymmetric Hydroacylation as the Key Step
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The
Asymmetric cyclisation of substituted pent-4-enals by a chiral rhodium phosphine catalyst
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194:
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Michael C. Willis (2009). "Transition Metal
Catalyzed Alkene and Alkyne Hydroacylation".
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Brian R. James, and
Charles G. Young Journal of Organometallic Chemistry Volume 285,
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Yukari Taura, Masakazu Tanaka, Xiao-Ming Wu, Kazuhisa
Funakoshi and Kiyoshi Sakai.
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The reaction was discovered in the 1970s as part of a synthetic route to certain
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416:
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Yukari Tauraa, Masakazu
Tanakaa, Kazuhisa Funakoshia and Kiyoshi Sakai.
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Brian R. James and
Charles G. Young J. Chem. Soc., Chem. Commun.,
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This step can be followed by reductive elimination of the alkane:
511:
Patricia Marce, Yolanda Dıaz, M. Isabel Matheu, Sergio
Castillon
257:
30:
inserts into a formyl C-H bond. With alkenes, the product is a
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265:
31:
451:
Asymmetric cyclization reactions by Rh(I) with chiral ligands
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Transition-Metal-Promoted
Aldehyde-Alkene Addition Reactions
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Labeling studies establish the following regiochemistry:
132:. In this reaction the solvent was saturated with
124:application involved cyclization of 4-pentenal to
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54:With an alkyne instead, the reaction produces an
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69:. It is almost invariably practiced as an
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77:, often based on rhodium phosphines.
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264:. In one application the ligand is
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380:Charles F. Lochow, Roy G. Miller
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300:, 8th ed. Rxn. 15-30.
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93:and a stoichiometric amount of
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473:
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61:The reaction requires a metal
1:
498:10.1016/S0040-4020(01)80954-6
469:10.1016/S0040-4039(01)93891-2
365:10.1016/S0040-4039(01)84569-X
280:
189:, hydroacylation begins with
440:10.1016/0022-328X(85)87377-0
113:was formed as the result of
7:
10:
559:
80:
298:March's Organic Chemistry
248:Asymmetric hydroacylation
519:, 10 (21), pp 4735–4738
233:-H → R"-H + M(CO)L
89:. The reaction required
488:. Volume 47, Issue 27,
459:. Volume 30, Issue 46,
388:, 98 (5), pp 1281–1283
260:catalysts and a chiral
71:intramolecular reaction
28:unsaturated hydrocarbon
56:α,β-unsaturated ketone
252:Hydroacylation as an
203:reductive elimination
109:An equal amount of a
75:homogeneous catalysts
417:10.1039/C39830001215
195:carbon-hydrogen bond
130:Wilkinson's catalyst
95:Wilkinson's catalyst
456:Tetrahedron Letters
394:10.1021/ja00421a050
352:Tetrahedron Letters
254:asymmetric reaction
199:migratory insertion
177:=CHR' → RC(O)CH
42:=CHR' → RC(O)CH
492:, Pages 4879-4888
463:, Pages 6349-6352
262:diphosphine ligand
217:-H → R"-M(CO)L
191:oxidative addition
187:reaction mechanism
165:Reaction mechanism
543:Organic reactions
525:10.1021/ol801791g
382:J. Am. Chem. Soc.
359:(13): 1287–1290.
328:10.1021/cr900096x
193:of the aldehydic
91:tin tetrachloride
67:radical initiator
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527:
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185:In terms of the
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21:organic reaction
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115:decarbonylation
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322:(2): 725–748.
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296:Smith (2020),
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128:using (again)
126:cyclopentanone
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17:Hydroacylation
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152:CHO → (CH
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111:cyclopropane
108:
84:
60:
53:
23:in which an
16:
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485:Tetrahedron
173:RCDO + CH
87:prostanoids
38:RCHO + CH
513:Org. Lett.
316:Chem. Rev.
281:References
120:The first
266:Me-DuPhos
229:R"-M(CO)L
213:R"C(O)-ML
122:catalytic
537:Category
336:19873977
134:ethylene
63:catalyst
258:rhodium
81:History
334:
73:using
32:ketone
181:CHDR'
144:=CHCH
65:or a
517:2008
490:1991
461:1989
432:1985
409:1983
386:1976
332:PMID
521:doi
494:doi
465:doi
436:doi
413:doi
390:doi
361:doi
324:doi
320:110
136:.
34::
539::
515:,
384:,
357:13
355:.
330:.
305:^
289:^
268::
221:-H
209::
160:CO
148:CH
140:CH
117:.
97::
58:.
50:R'
46:CH
523::
496::
467::
438::
415::
392::
367:.
363::
338:.
326::
235:n
231:n
219:n
215:n
179:2
175:2
158:4
156:)
154:2
150:2
146:2
142:2
48:2
44:2
40:2
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