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1	Theoretical Studies on Acetylenic Scaffolds	1
1.1	Introduction	1
1.2	Linear Acetylenic Scaffolds	2
1.2.1	The Dicarbon Molecule and Acetylene	2
1.2.2	Uncapped pure sp Carbon Chains	3
1.2.3	Capped all-sp Oligoacetylenic Chains	5
1.2.4	Hybrid sp-sp² Oligoacetylenic Molecules	9
1.2.5	Hybrid sp-sp³ Oligoacetylenic Molecules	14
1.3	Cyclic Acetylenic Scaffolds	15
1.3.1	Hybrid sp-sp³ Rings	15
1.3.2	Hybrid sp-sp² Rings (Dehydroannulenes)	20
1.3.3	carbo-Heteroannulenes	32
1.4	Star-Shaped Acetylenic Scaffolds	34
1.4.1	Atomic Cores	34
1.4.2	Rod Cores	34
1.4.3	Cyclic Cores	37
1.5	Cage Acetylenic Scaffolds	40
1.5	Conclusion	41
	Acknowledgements	42
2	Synthesis of Heterocycles and Carbocycles by Electrophilic Cyclization of Alkynes	51
2.1	Introduction	51
2.2	Cyclization of Oxygen Compounds	51
2.2.1	Cyclization of Acetylenic Alcohols	51
2.2.2	Cyclization of Acetylenic Phenols	55
2.2.3	Cyclization of Acetylenic Ethers	57
2.2.4	Cyclization of Acetylenic Acids and Derivatives	59
2.2.5	Cyclization of Acetylenic Aldehydes and Ketones	63
2.3	Cyclization of Sulfur and Selenium Compounds	66
2.4	Cyclization of Nitrogen Compounds	67
2.4.1	Cyclization of Acetylenic Amines	67
2.4.2	Cyclization of Acetylenic Amides	70
2.4.3	Cyclization of Acetylenic Carbamates	73
2.4.4	Cyclization of Acetylenic Sulfonamides	75
2.4.5	Cyclization of Acetylenic Enamines and Imines	77
2.4.6	Cyclization of Other Acetylenic Nitrogen Functional Groups	79
2.5	Cyclization of Carbon onto Acetylenes	81
2.5.1	Cyclization of Acetylenic Carbonyl Compounds and Derivatives	81
2.5.2	Cyclization of Diacetylenes	83
2.5.3	Cyclization of Aryl Acetylenes	84
2.5.4	Cyclization of Acetylenic Organometallics	89
2.6	Conclusions	90
2.7	Representative Experimental Procedures	90
2.7.1	Synthesis of -Methylene--butyrolactones by Carbonylation of 1-Alkyn-4-ols	90
2.7.2	Synthesis of 1-Alkoxyisochromenes by Cyclization of 2-(1-Alkynyl) benzaldehydes	90
2.7.3	Synthesis of 3-Aryl(vinylic)indoles by Palladium-catalyzed Cross-coupling of Aryl Halides or Vinylic Triflates and 2-(1-Alkynyl)trifluoroacetanilides	90
2.7.4	Synthesis of Pyridines by the Gold-catalyzed Cross-coupling of Ketones and Propargyl Amine	91
2.7.5	Synthesis of 4-Iodoisoquinolines by the Cyclization of Iminoalkynes	91
2.7.6	Synthesis of Cyclic Amines by Acetylene-Iminium Ion Cyclizations	91
	Acknowledgements	92
3	Addition of Terminal Acetylides to CO and CN Electrophiles	101
3.1	Introduction	101
3.2	Background	103
3.3	Additions with Stoichiometric Amounts of Metal Acetylides	106
3.4	Nucleophilic CO Additions involving the use of Zn(ii) Salts	114
3.5	Acetylene Additions to CN Electrophiles	125
3.6	Conclusion	131
3.7	Experimental Procedures	131
3.7.1	General Procedure for the Enantioselective Alkynylation of Aldehydes by the use of Stoichiometric Amounts of Zn(OTf)₂	131
3.7.2	General Procedure for the Zn(OTf)₂-Catalyzed Enantioselective Alkynylation of Aldehydes	132
3.7.3	General Procedure for the Enantioselective Alkynylation of Ketones Catalyzed by Zn(salen) Complexes	132
3.7.4	General Procedure for the Zn(OTf)₂-Catalyzed Diastereoselective Alkynylation of N-Glycosyl Nitrones	133
3.7.5	General Procedure for the Et₂Zn-Catalyzed Diastereoselective Alkynylation of Chiral Nitrones	133
3.7.6	General Procedure for the CuBr-Catalyzed Enantioselective Preparation of Propargylamines	133
3.7.7	General Procedure for the [IrCl(COD)]₂-Catalyzed Alkynylation of Imines	134
4	Transition Metal Acetylides	139
4.1	Introduction	139
4.2	General Comments	140
4.2.1	Structure and Bonding	140
4.2.2	Syntheses	141
4.2.3	Reactions	144
4.3	Titanocene- and Zirconocene-Acetylides	146
4.3.1	MCCR	146
4.3.2	M(CCR)₂	148
4.3.3	M(CCR)₃	148
4.3.4	Products of [Cp₂M(²-RC₂R)] and [Cp*₂M(²-RC₂R)] with Acetylenes	149
4.3.5	Reactions	151
4.4	Complexation of MCCM	160
4.4.1	Examples	160
4.4.2	Molecular Dynamics of Acetylides	161
4.4.3	Acetylides in the Topomerization of Alkynes	163
4.5	Summary and Outlook	165
4.6	Typical Experimental Procedures	166
4.6.1	Synthesis of a Monomeric Ti(iii) Monoacetylide [Cp*₂TiCCtBu]	166
4.6.2	Synthesis of a Ti(iii) Bisacetylide Tweezer [Cp₂Ti(CC^tBu) ₂][Li(THF)]	166
4.6.3	Synthesis of a Dinuclear Ti(iii) Monoacetylide [Cp₂TiC₂SiMe₃)]₂ by CC Cleavage of a 1,3-Butadiyne	167
4.6.4	Synthesis of a Zr(iv) Bisacetylide [Cp*₂Zr(CCSiMe₃)₂]	167
4.6.5	Synthesis of a Zirconacyclocumulene [Cp*₂Zr(⁴ -1.2.3.4-Me₃SiC₄SiMe₃)]	167
	Acknowledgment	168
5	Acetylenosaccharides	173
5.1	Introduction	173
5.2	Isolation of Acetylenosaccharides from Natural Sources	174
5.3	Preparation of Monoalkynylated Acetylenosaccharides	177
5.3.1	Preparation of Linear Acetylenosaccharides	177
5.3.2	Preparation of Branched-Chain Acetylenosaccharides	188
5.4	Preparation of Dialkynylated Acetylenosaccharides	193
5.4.1	Linear Dialkynylated Acetylenosaccharides	193
5.4.2	Branched Dialkynylated Acetylenosaccharides	194
5.4.2.1	4-O-Alkynyl--_Dglucopyranosylacetylenes	195
5.5	Transformations of Acetylenosaccharides	203
5.5.1	Ring-Forming Reactions	204
5.5.2	Coupling Reactions	212
5.5.2.1	Homocoupling of Acetylenosaccharides	213
5.6	Biological and Medicinal Uses of Acetylenosaccharides	215
5.7	Experimental Protocols	215
	Acknowledgement	219
6	Semiconducting Poly(arylene ethylene)s	233
6.1	Introduction	233

6.2	Synthesis	234
6.3	Conducting Properties of PArEs	236
6.4	Photophysical Properties and Interpolymer Electronic Interactions	238
6.5	Sensor Applications	247
6.6	Superstructures	249
6.7	Summary	255
6.8	General Procedures for Synthesis of PPEs	255
	Acknowledgement	256
7	Polyynes via Alkylidene Carbenes and Carbenoids	259
7.1	Introduction	259
7.2	Alkylidene Carbene and Carbenoid Species	260
7.3	Alkyne Formation from Carbenes and Carbenoids	261
7.3.1	Synthesis of Acetylenes: the Fritsch–Buttenberg–Wiechell Rearrangement	261
7.3.2	Synthesis of 1,3–Butadiynes	265
7.3.3	Synthesis of 1,3,5–Hexatriynes	268
7.3.4	Tri- and Pentaynes from Free Alkylidene Carbenes	273
7.4	Toward applications	274
7.4.1	Natural Products Synthesis	274
7.4.2	Extended Arylenethynylene Derivatives	276
7.4.3	Cyclo[n]carbons	283
7.5	Linear Conjugated Polyynes	284
7.5.1	Synthesis of Triisopropylsilyl End-Capped Polyynes	285
7.5.2	Solid-State Characterization	289
7.5.3	Linear Optical Properties	291
7.5.4	Third-Order Nonlinear Optical Properties	294
7.6	Conclusions	296
7.7	Experimental procedures	297
7.7.1	General procedure for Friedel–Crafts Acylation	297
7.7.2	General Procedure for Dibromoolefination	297
7.7.3	General FBW Rearrangement Procedure	297
7.7.4	General Oxidative Coupling Procedure	298
	Acknowledgements	298
8	Macrocycles Based on Phenylacetylene Scaffolding	303
8.1	Introduction	303
8.2	Synthetic Strategies	304
8.2.1	Intermolecular Approach	304
8.2.2	Intramolecular Approach	307
8.2.3	Comparison of the Two Pathways	311
8.3	Phenylacetylene Macrocycles	312
8.3.1	Ortho PAMs	312
8.3.2	Meta-PAMs	323
8.3.3	Para-PAMs	334
8.3.4	Mixed PAMs	335
8.4	Phenyldiacetylene Macrocycles	338
8.4.1	Ortho-PDMs	339
8.4.2	Meta-PDMs	356
8.4.3	Para-PDMs	361
8.4.4	Mixed PDMs	362
8.5	Phenyltriacetylene Macrocycles	373
8.6	Phenyltetraacetylene Macrocycles	374
8.7	Phenyloligoacetylene Macrocycles	377
8.8	Conclusions	378
8.9	Experimental	378
8.9.1	Preparation of 8 From [(t-BuO) ₃WCt-Bu)] Catalysis of 13	378
8.9.2	Synthesis of 8 and 10 from Copper (2-Iodophenyl)acetylide	379
8.9.3	Preparation of 31 by Pd-catalyzed Cyclization of 29	379
8.9.4	Preparation of 122 by Pd-mediated Cyclization of 136	379
8.9.5	Synthesis of 148 from 149 and Mo(CO) ₆	380
8.9.6	Preparation of 189 and 190 from 1,2-Diiodotetrafluorobenzene under Hay Conditions	380
8.9.7	Preparation of 1 by Deprotection and Cyclization of 223	380
8.9.8	Synthesis of 304 by Photolysis of Dewar Benzene 305	381
8.9.9	Preparation of 332 and 333 by Deprotection/Cyclization of 335 in situ	381
	Acknowledgments	381
9	Carbon-Rich Compounds: Acetylene-Based Carbon Allotropes	387
9.1	Introduction	387
9.2	Linear Carbon Clusters	388
9.3	Carbyne	394
9.4	Linear Polyynes	397
9.5	Monocyclic Carbon Clusters: Cyclo[n]carbons	410
9.6	Three-Dimensional Multicyclic Polyynes	415
9.7	Conclusion	420
	Acknowledgement	420
10	Shape-Persistent Acetylenic Macrocycles for Ordered Systems	427
10.1	Introduction	427
10.2	Ordered Systems	429
10.2.1	Host-Guest Complexes	429
10.2.2	Tubular Superstructures in Solution	433
10.2.3	Thermotropic Liquid Crystals	438
10.2.4	Two-Dimensional Organization	442
10.3	Conclusions	446
10.4	Experimental Procedures	447
10.4.1	Deprotection of a CPDMS-Protected Acetylene	447
10.4.2	Template-based Oxidative Cyclodimerization of a Rigid Bisacetylene	447
10.4.3	Deprotection of a Macrocyclic THP-Protected Tetraphenol	448
10.4.4	Alkylation of a Macrocyclic Tetraphenol	448
10.4.5	Hydrolysis of a Macrocycle with Two Intraannular Ester Groups	448
10.4.6	ormation of a Macrocycle with Two Intraannular Thioether Groups	449
	Acknowledgement	449
11	Chiral Acetylenic Macromolecules	453
11.1	Introduction	453
11.2	Chiral Acetylenic Dendrimers	454
11.3	Chiral Acetylenic Polymers	460
11.3.1	Chiral Polymers Containing Main-Chain para-Phenyleneethynylenes	460
11.3.2	Chiral Polymers Containing Main-Chain ortho-Phenyleneethynylenes	468
11.3.3	Chiral Polymers Containing Main-Chain meta-Phenyleneethynylenes	482
11.3.4	Chiral Polymers Containing Main-Chain Thienylene-Ethynylenes	483
11.3.5	Chiral Polymers Containing Side-Chain Phenyleneethynylenes	485
11.4	Summary	490
	Acknowledgements	491
11.5	Experimental Procedures	491
11.5.1	Preparation of the Chiral Dendrimers – A Typical Procedure	491
11.5.2	Preparation of the Chiral Polymer (R)-18e	491
11.5.3	Preparation of the Chiral Polymer (R)-45	492
11.5.4	Preparation of the Helical Polymer (R)-85	492

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